JP2709649B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a high-contrast, high-sensitivity negative image and a good halftone dot image quality. The present invention relates to a silver halide photographic material.

(Prior Art) Conventionally, a group of compounds capable of releasing a photographically useful group via an oxidation-reduction reaction is known.

Recent examples include JP-A-61-213847 and JP-A-61-2788.
No. 52, No. 62-296,138, No. 64-66641, No. 64-88451 and the compounds described in U.S. Pat. No. 4,684,604.

The compounds known so far as described in the above patents are used for various purposes depending on the type of each photographically useful group.

For example, in the field of silver halide photographic materials for photoengraving, in this field, the variety of printed matter,
In order to cope with the complexity, there is a demand for a photographic light-sensitive material having good original reproducibility, a stable processing solution, or a simple replenishment.

Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, images having different densities and cotton widths are mixed in the original, and a plate-making camera, a photographic material, or an image forming method for finishing these originals with good reproduction is strongly desired. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinkage) of a halftone picture is widely performed, and in plate making using enlarged halftone dots, the number of lines becomes coarse and blurred. Shooting. In the reduction, the number of lines / inch is larger than that of the original, and a thin point is photographed. Therefore, there is a demand for an image forming method having a wider latitude in order to maintain the reproducibility of halftone.

A halogen lamp or a xenon lamp is used as a light source of a plate making camera. In order to obtain a photographic sensitivity with respect to these light sources, a photographic light-sensitive material is usually subjected to orthosensitization. However, it has been found that the ortho-sensitized photographic material is more strongly affected by the chromatic aberration of the lens, so that the image quality is liable to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

As a system that meets the demands of a wide latitude, the effective concentration of sulphite ions in a lithographic silver halide photosensitive material composed of silver chlorobromide (at least silver chloride content of 50% or more) is extremely low (usually 0.1 mol / l or less). There is known a method of obtaining a line image or a halftone image having a high contrast and a high blackening density in which an image portion and a non-image portion are clearly distinguished by processing with a hydroquinone developer. However, in this method, since the concentration of sulfurous acid in the developer is low, development is extremely unstable against air oxidation, and various efforts and efforts have been made to keep the solution activity stable. Was extremely slow, and the work efficiency was reduced at present.

For this reason, an image forming system that eliminates instability of image formation by the above-described developing method (lith developing system), develops with a processing solution having good storage stability, and obtains ultra-high contrast photographic characteristics is provided. U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857, and
4,224,401, 4,243,739, 4,272,606, 4,3
As seen in No. 11,781, the surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added contains a sulfurous acid preservative at pH 11.0 to 12.3 and 0.15 mol / l or more, and has good storage stability. Is treated with a developing solution having
Systems have been proposed for forming over 10 ultra-high contrast negative images. This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is.

Although the above imaging system shows excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, the original reproducibility has been further improved to cope with the recent variety of printed matter. A system is desired.

Attempts to improve image quality include, for example,
A method of releasing a development inhibitor from a redox compound having a carbonyl group disclosed in No. 7 or the like like a silver image is known. However, even when these compounds are used, the halftone gradation is insufficiently elongated.

Therefore, there has been a demand for development of a photosensitive material which forms a hard halftone dot image using a stable developer and has a wide tone control of the image.

On the other hand, in the work of plate collecting and reversing processes, work efficiency has been improved by working in a brighter environment, and therefore, it is necessary to work in an environment that can be substantially called a bright room The development of photosensitive materials for plate making and the development of exposure printers have been promoted.

The light-sensitive material for a bright room described in the present patent is a light-sensitive material which does not contain an ultraviolet light component and has a wavelength of substantially not less than 400 nm and which can be safely used as safe light for a long time.

The light-sensitive room light-sensitive material used in the plate-collecting and reversing processes is a film-developed film on which characters or halftone images are formed. A photosensitive material used to perform positive image conversion or positive image / positive image conversion. A halftone image / line image and character image are converted to a negative image / positive image according to their halftone dot area, line width and character image width, respectively. It is required to have the ability to perform image conversion. It is required to have the ability to adjust the tone of a halftone dot image and the line width of a character line image.

However, in the advanced image conversion work of character extraction image formation by repetition, the conventional method using the light room reversing process using the light-sensitive material for the bright room uses the conventional dark room reversing process using the dark room reversing photosensitive material. Compared with the method, there is a disadvantage that the quality of the character-extracted image is deteriorated.

A more detailed description of the method of forming a character-extracted image by overlapping is as shown in FIG. 1, where a transparent or translucent pasting base (a) and (c) is used.
(A polyethylene terephthalate film having a thickness of about 100 μm is usually used) and a film on which a character or line image is formed (line drawing manuscript) (b)
And a film on which a dot image is formed (dot document)
(D) is superimposed on the original,
The exposure is performed by bringing the emulsion surface of the return photosensitive material (e) into close contact with the halftone dot document (d).

A post-exposure development process is performed to form a white part of a line image in a halftone dot image.

An important point in such a method for forming a character-extracted image is that the negative image / positive image conversion is ideally performed in accordance with the halftone dot area and the line width of each of the halftone original and the line drawing original. However, as is apparent from FIG. 1, the halftone original is exposed in direct contact with the emulsion surface of the return photosensitive material, whereas the halftone original (c) and the halftone original ( D) is exposed to the return photosensitive material through the middle.

Therefore, if an exposure amount for faithfully converting a halftone dot document into a negative image / positive image is given, the line image document becomes out-of-focus exposure via the spacer by the pasting base (c) and the halftone document (d). The width of the image in the white part of the image becomes narrow. This is the cause of the deterioration of the quality of the extracted character image.

To solve the above problems, systems using hydrazine are disclosed in JP-A-62-80640, JP-A-62-235938, and JP-A-62-235939.
Nos. 63-104046, 63-103235, 63-296031,
Nos. 63-314541 and 64-13545,
Although not enough, further improvement is desired.

As a method of using a redox compound that releases a development inhibitor in a photoengraving system using a hydrazine compound as a nucleating agent, JP-A-56-153,336, JP-A-61-213,847,
The methods described in JP-A-62-296,138, JP-A-64-72,139, and JP-A-64-72,140 are known. Various development inhibitors are described as development inhibitors for these redox compounds.
As a nucleation development inhibitor effective for a nucleation development system using a nucleation agent, there is no suggestion as to which development inhibitor is particularly effective for suppressing the nucleation development system.

A redox compound that releases a development inhibitor containing a nitro group, an anion group, and a pyridine group in a partial structure is described as being effective in a nucleation development system, but a sufficiently effective suppression effect is not necessarily achieved in a nucleation development system. Not obtained.

The nucleation infectious development is carried out by Fujifilm GRANDEX system (Fuji Photo Film Co., Ltd. and Kodak Ultratec system (East
man Kodak Co., Ltd.) is a new development chemistry used in the image forming method. This development chemistry
"Journal of the Photographic Society of Japan", Vol. 52, No. 5, pp. 390-394 (1989) and "Journal of Photographic Science", 35
Vol. 162 (1987), developing the exposed silver halide grains with a normal developing agent,
A nucleation active species is generated based on the cross-oxidation of the oxidizing product of the developing agent and the nucleating agent, and the nucleation transmission of the peripheral unexposed to weakly exposed silver halide particles by the active species. It consists of two steps of development.

Therefore, the entire development process is a sum of the normal development process and the nucleation development process. Compounds that inhibit the process can exert an inhibitory effect. The latter is referred to herein as a nucleation development inhibitor.

(Object of the Invention) A first object of the present invention is to provide a novel redox compound which releases a nucleation development inhibitor effective for a nucleation development system.

A second object of the present invention is to provide a novel redox compound which is excellent in storage stability and has a rapid release of a nucleation development inhibitor.

A third object of the present invention is to provide a photographic light-sensitive material having a wide exposure latitude in line drawing, a super-high contrast (particularly, a γ value of 10 or more) and a high resolution.

A fourth object of the present invention is to provide an ultra-high contrast photographic material which reproduces a line image well and has a high background density (Dmax).

A fifth object of the present invention is to provide an ultra-high contrast photographic light-sensitive material which has a wide exposure latitude in halftone dot photography, a high density, a clear halftone dot outline, and a uniform dot quality. It is to be.

(Constitution of the Invention) The objects of the present invention have been attained by a silver halide photographic material characterized by containing a redox compound capable of releasing a nucleation development inhibitor by being oxidized.

The redox compound of the present invention that can release a nucleation inhibitor by being oxidized will be described.

The redox group of the redox compound is preferably a hydroquinone, a catechol, a naphthohydroquinone, an aminophenol, a pyrazolidone, a hydrazine, a droxylamine, or a reductone, and more preferably a hydroxy.

The hydrazines used as a redox compound capable of releasing a nucleation inhibitor by being oxidized according to the present invention are preferably represented by the following general formula (R-1) or (R-
2), represented by the general formula (R-3). The general formula (R-
The compound represented by 1) is particularly preferred.

General formula (R-1) General formula (R-2) General formula (R-3) In these formulas, R ₁ represents an aliphatic group or an aromatic group.

Represents G ₂ is a mere bond, -O-, -S- or And R ₂ represents a group or a hydrogen atom having the same definition as that of R _1, and when a plurality of R ₂ are present in a molecule, they may 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 synonymous with A ₁ or Represents

A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R ₁ (in this case, two -G ₁ -G _2-
R ₁ may be the same or different. ).

Time represents a divalent linking group, and t represents 0 or 1. PUG represents a nucleation inhibitor. However, PUG does not represent a nucleating development inhibitor having a nitro group, an anion group, or a pyridine group as a partial structure. Here, the anion group includes a sulfo group, a carboxy group, etc., as disclosed in Japanese Patent Application No. 2-64,717.
Indicates what is described in the item.

General formulas (R-1), (R-2) and (R-3) will be described in more detail.

In formulas (R-1), (R-2) and (R-3), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms.
And particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. 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 unsaturated heterocyclic group. Here, the unsaturated 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 and an isoquinoline ring. Among them, those containing a benzene ring are preferred.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated 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 group,
Urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy Group, a carbonamido group, a sulfonamido group, a carboxyl group, a phosphoric acid amide group and the like. Preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (Preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 30 carbon atoms), a substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with 30 alkyl groups), 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 A compound having 1 to 40, a phosphoric acid amide group (preferably having 1 to 40 carbon atoms) and the like.

G ₁ in the general formulas (R-1), (R-2) and (R-3) is -SO ₂ - group are preferred, Is most preferred.

A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, Is preferred.

In the general formulas (R-1), (R-2) and (R-3)
Time represents a divalent linking group, and may have a timing adjusting function.

The divalent linking group represented by Time represents a group capable of releasing PUG in one or more steps of Time-PUG released from the oxidized form of the redox nucleus.

Examples of the divalent linking group represented by Time include U.S. Pat. Nos. 4,310,612 (JP-A-55-53,330) and 4,35,330.
P by the intramolecular ring closure reaction after ring cleavage described in
Those releasing UG; U.S. Pat. Nos. 4,330,617 and 4,446,2
No. 16 and 4,483,919, with the formation of an acid anhydride by an intramolecular ring-closure reaction of the carboxyl group of succinic acid monoester or an analog thereof described in JP-A-59-121,328, etc.
Those that release G; U.S. Pat. Nos. 4,409,323 and 4,421,84
No. 5, Research Disclosure Magazine No. 21, 228 (1981)
No. 4,416,977 (JP-A-57-135,941).
No. 4), JP-A-58-209,736, JP-A-58-209,738 and the like to produce quinomonomethane or an analog thereof by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group. US Pat. No. 4,420,554 (JP-A-57-136,640), JP-A-57-135,
No. 945, No. 57-188,035, No. 58-98,728 and No. 58-20
Those which release PUG from the γ-position of an enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocycle described in JP-A-9,737; conjugated with a nitrogen atom of a nitrogen-containing heterocycle described in JP-A-57-56,837 Which releases PUG by an intramolecular ring-closure reaction of an oxy group generated by electron transfer to a carbonyl group; US Pat. No. 4,146,396 (JP-A-52-90932)
JP-A-59-93,442, JP-A-59-75475, JP-A-69-1
No. 0-249148, JP-A-60-249149, etc., which release PUG with formation of aldehydes; JP-A-51-146,82.
No. 8, No. 57-179,842 and No. 59-104,641, which release PUG with decarboxylation of carboxyl group; -O-COOC
It has the structure of R _a R _b -PUG (R _a and R _b represent a monovalent group), and is accompanied by decarboxylation and subsequent formation of aldehydes.
Which release PUG with the formation of isocyanate described in JP-A-60-7,429; U.S. Pat.
38 and 193, which release PUG by a coupling reaction with an oxidized color developer.

The divalent group represented by Time in the general formulas (R-1), (R-2) and (R-3) is preferably the following general formula (T-
From 1), it is represented by the general formula (T-6). In these, ** indicates the site where Time binds to PUG, and * indicates the other site.

General formula (T-1) Wherein W is an oxygen atom, a sulfur atom or Wherein R ₂₁ and R ₂₂ represent a hydrogen atom or a substituent, R ₂₃ represents a substituent, and t represents 1 or 2. When t is 2, two Represents the same or different. R ₂₁ and R
_{When 22} represents a substituent and representative examples of R ₂₃ are R ₂₄ , R ₂₄ CO—, R ₂₄ SO ₂ —, Or And the like. Here, R ₂₄ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₂₅ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.

Each of R ₂₁ , R ₂₂ and R ₂₃ represents a divalent group, and includes the case where they are linked to form a cyclic structure. General formula (T
Specific examples of the group represented by -1) include the following groups.

Formula (T-2) * -Nu-Link-E-** wherein Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and Nu represents an electrophilic group. Link is a group that can undergo a more nucleophilic attack and cleave the bond with the ** mark.
Nu represents a linking group that sterically relates to E so that an intramolecular nucleophilic substitution reaction can occur. General formula (T-2)
Specific examples of the group represented by are, for example, the following.

General formula (T-3) In the formula, W, R ₂₁ , R ₂₂ and t have the same meanings as described for (T-1). Specific examples include the following groups.

General formula (T-4) General formula (T-5) General formula (T-6) In the formula, W and R ₂₁ have the same meaning as described in formula (T-1). Specific examples of the group represented by the general formula (T-6) include the following groups.

Further, as the Time, the general formula (T-1) to the general formula (T-
Groups formed by combining a plurality of groups represented by 6) are also useful. Preferred examples thereof are shown below. *, *
* Has the same meaning as in formulas (T-1) to (T-6).

Specific examples of the divalent linking group represented by Time are also described in detail in JP-A-61-236,549, JP-A-64-88451, and Japanese Patent Application No. 63-98,803.

PUG represents Time _t PUG or a group having a nucleation development inhibitory effect as PUG. The nucleation development inhibitor represented by PUG has a hetero atom, and is bonded via the hetero atom,
A nitroso group as a substituent or part of a substituent, (Halogen represents a bromine atom, a chlorine atom, etc., R ₃₁ represents a hydrogen atom, a halogen atom.), Quinones (for example, benzoquinone, naphthoquinone, quinone monoiminequinone diimine, etc.), and fused pyridines (for example, , Quinoline, phenanthroline, acridine and the like), pyrazines (for example, quinoxalin, phenazine and the like), tetrazoliums, amine oxides (for example, pyridine oxide and the like), azoxy compounds, oxidizing coordination compounds (for example, Fe ^III chelate compound).

Preferred groups represented by PUG are those represented by the general formula (P-
1) or represented by the general formula (P-2).

Formula (P-1) -X ₁ X _{2 m} X _{3 In the} formula, X ₁ represents —O—, —S—, —Se—, —NR ₃₂ —, and R ₃₂ represents a hydrogen atom or a general formula ( The group is the same as defined for R ₁ in P-1). X ₂ is an aliphatic group, an aromatic group,
Alternatively, these groups and -O-, -S-, -Se-, -NR ₃₃
- (R ₃₃ is as defined for R ₃₂₎ -SO -, - SO ₂ - a divalent group formed by combining, may be substituted. Preferred substituents are the same as those exemplified as the substituent for R _{1 in} formula (R-1). X ₃ is a nitroso group mentioned as a substitution of PUG, Examples include quinones, condensed pyridines, pyrazines, tetrazoliums, amine oxides, azoxy compounds, oxidizing coordination compounds, and the like, and may be further substituted. Preferred substituents are the same as those exemplified as the substituent for R _{1 in} formula (R-1). m is 1, but when X ₃ represents a quinone, a condensed pyridine, a pyrazine, a tetrazolium, an amine oxide, an azoxy compound, or a coordinating compound having an oxidizing ability, it may be 0. good.

General formula (P-2) In the formula, X ₂ and X ₃ have the same definition as in the general formula (P-1).
₄ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring together with a nitrogen atom. n represents 0 or 1.

In the general formula (P-2) Is preferably a heteroaromatic ring. Further, these heteroaromatic rings are preferably 5- or 6-membered rings, and may be monocyclic or condensed, or may be substituted. Representative examples of preferred heteroaromatic rings include, for example, pyrrole, imidazole, pyrazole, 1,
2,3-triazole, 1,2,4-triazole, tetrazole, 2-thioxathiazoline, 2-oxathiazoline,
2-thioxoxazoline, 2-oxoxazoline,
2-thioximidazoline, 2-oxaimidazoline,
3-thioxa-1,2,4-triazoline, 3-oxa-1,2
-4-triazoline, 1,2-oxazoline-5-thione, 1,2-thiazoline-5-thione, 1,2-oxazoline-5-one, 1,2-thiazoline-5-one, 2-thioxa-1 , 3,4-thiadiazoline, 2-oxa-1,3,4-thiadiazoline, 2-thioxa-1,3,4-oxadiazoline, 2-oxa-1,3,4-oxadiazoline, 2-thio Oxadihydropyridine, 2-oxadihydropyridine,
4-thioxadihydropyridine, 4-oxadihydropyridine, isoindole, indole, indazole,
Benzotriazole, benzimidazole, 2-thioxabenzimidazole, 2-oxabenzimidazole, benzoxazoline-2-thione, azaindenes, benzoxazolin-2-one, benzothiazoline-2-thione, benzothiazolin-2-one, Carbazole, purine, carbolin, phenoxazine, phenothiazine, pyrazolopyridines at various fused positions, pyrazolopyrimidines, pyrazolopyrroles, pyrazolopyrazoles, pyrazoloimidazoles, pyrazolooxazoles, pyrazolothiazole , Pyrazolotriazoles, imidazolopyridines, imidazolopyrimidines,
Examples thereof include imidazolopyrroles, imidazoloimidazoles, imidazolooxazoles, imidazolothiazoles, and imidazolotriazoles.

More preferred heteroaromatic rings include, for example, pyrrole,
Imidazole, pyrazole, triazole, tetrazole, 2-thioxathiazoline, 2-thioxoxazoline, indole, indazole, benzotriazole,
Benzimidazole, 2-thioxa-1,3,4-thiadiazoline, azaindene, 5-thioxa-tetrazoline,
2-thioxa-1,3,4-oxadiazoline, 3-thioxa-1,2,4-triazoline, pyrazolopyridines at various condensed ring positions, pyrazoloimidazoles and the like, and particularly preferably pyrazole, It is a heteroaromatic ring containing a pyrazole skeleton like indazole and pyrazolopyridine.

These heterocyclic compounds may have a substituent.
Examples of the substituent include a mercapto group, a hydroxy group,
Alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, Sulfonyl group,
Examples include a sulfinyl group, a halogen atom, a cyano group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, and a phosphonamido group.

In the general formulas (R-1), (R-2) and (R-3), R ₁ or Time _t PUG represents a ballast group commonly used in immobile photographic additives such as couplers. A group which promotes the compounds represented by formulas (R-1), (R-2) and (R-3) to be adsorbed to silver halide may be incorporated.

The ballast group has the general formula (R-1), (R-2), (R-
An organic group that gives a molecular weight sufficient to prevent the compound represented by 3) from substantially diffusing into another layer or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, It comprises one or more combinations of an amide group, a ureido group, a urethane group, a sulfonamide group and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the group for promoting 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 Cyclic thioamide groups such as oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione, and chain thioamides Group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom, this is synonymous with a cyclic thioamide group having a tautomeric relationship with the nitrogen atom) Specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazo Le, indazole, benzimidazole, imidazole, benzothiazole,
Nitrogen, oxygen, such as thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene,
Examples thereof include a 5- or 6-membered nitrogen-containing heterocyclic group composed of a combination of sulfur and carbon, and a heterocyclic quaternary salt such as benzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent of R ₁ .

Hereinafter, specific examples of the compound used in the present invention are listed, but the present invention is not limited thereto.

The synthesis of the redox compound used in the present invention is described, for example, in JP-A-61-213,847, JP-A-62-260,153, and U.S. Pat.
No. 4,604, Japanese Patent Application No. 63-98,803, U.S. Pat.No. 3,379,529
Nos. 3,620,746, 4,377,634, 4,332,878,
It can be synthesized according to the synthesis methods described in JP-A-49-129,536, JP-A-56-153,336, JP-A-56-153,342 and the like.

The compound of the general formula (R-1) of the present invention can be generally synthesized by the following route. That is, the corresponding 2 equivalent PU
GTime) Is _t- H reacted with trichloromethyl chlorocarbonate in an organic solvent such as THF in the presence of a base such as triethylamine to form a symmetric carbonyl compound, and then reacted with the corresponding hydrazine compound (synthesis) Route 1) or after condensing the corresponding PUGTime _t H with p-nitrophenyl chlorocarbonate in the presence of a base,
Synthesized by reacting with the corresponding hydrazine compound (Synthetic route 2) The redox compound of the present invention is used in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ per mol of silver halide.
It is used in the range of １1 × 10 ^-2 mol.

The redox compound of the present invention may be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve 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. Objects can also be created and used. Alternatively, a redox compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The light-sensitive material of the present invention preferably uses a hydrazine derivative as a nucleating agent.

Examples of the nucleating agent preferably used in the present invention include hydrazine derivatives represented by the following general formula (I).

General formula (I) Wherein, R ₁₁ represents an aliphatic group or an aromatic group, R ₁₂
Is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
G ₁₁ represents an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group; Represents a thiocarbonyl group or an iminomethylene group;
₁₁ and A ₁₂ both represent a hydrogen atom or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (I), the aliphatic group represented by R ₁₁ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 30 carbon atoms.
20 linear, branched or cyclic alkyl groups. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

The aromatic group represented by R ₁₁ in the general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring,
Among them, there are benzothiazole rings and the like, and among them, those containing a benzene ring are preferable.

Particularly preferred as R ₁₁ is an aryl group.

The aryl group or unsaturated heterocyclic group represented by R ₁₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and a ureido. Group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, Acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide group, And the like. Preferred substituents are a straight-chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or 2-alkyl group having 1 to 3 carbon atoms in the alkyl portion). Ring), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 20 carbon atoms) 30), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) Stuff)

In formula (I), the alkyl group represented by R ₁₂ is preferably an alkyl group having 1 to 4 carbon atoms, and includes a halogen atom, a hydroxyl group, a cyano group, a carboxy group,
Sulfo group, alkoxy group, phenyl group, alkyl or arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group,
Sulfamoyl group, nitro group, heteroaromatic group, And the like, and these groups may be further substituted.

As the aryl group, a monocyclic or bicyclic aryl group is preferable, and for example, those containing a benzene ring. The aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, a sulfonyl group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably a monocyclic one, and the substituent includes a halogen atom.

As the amino group, an unsubstituted amino group and a group having 1 to 10 carbon atoms
Are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Preferred among the groups represented by R ₁₂ are those wherein G ₁₁ is Is a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, etc.), an aralkyl group (for example, o
-Hydroxybenzyl group), an aryl group (for example,
A phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, a 2-hydroxymethylphenyl group), and a hydrogen atom is particularly preferable.

When G ₁₁ is a —SO ₂ — group, R ₃₂ is an alkyl group (for example, a methyl group) or an aralkyl group (for example, o
-Hydroxybenzyl group), an aryl group (for example,
A phenyl group or the like or a substituted amino group (such as a dimethylamino group) is preferred.

If G ₁₁ is a -SO- group, preferably R ₃₂ is like cyanobenzyl group, methylthiobenzyl group, G ₁₁ is In the above case, R ₁₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, and particularly preferably a phenoxy group.

When G ₁₁ is an N-substituted or unsubstituted iminomethylene group, preferred R ₁₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R _12, the substituents listed for R ₁₁ can be applied.

As G _{11 in the} general formula (I), Is most preferred.

R ₁₂ also splits the G ₁₁ -R ₁₂ moiety from the residual molecule,
₁₁ -R ₁₂ parts of atoms may be such as to rise to cyclization reaction to form a cyclic structure containing a is such that it can specifically represented by the general formula (a).

In the general formula (a) -R ₁₃ -Z ₁₁ Formula, Z ₁₁ is nucleophilically attacked to G _11, G ₁₁ -R ₁₃ -Z
R ₁₃ is a group that can cleave the ₁₁ moiety from the residual molecule,
Which was removing one hydrogen atom from _12, Z ₁₁ is a nucleophilic attack to _{G 11, G 11, R 13} , ring structures with Z ₁₁ is capable product.

More specifically, Z ₁₁ easily undergoes a nucleophilic reaction with G ₁₁ when the hydrazine compound of the general formula (I) produces the next reaction intermediate by oxidation or the like, and R ₁₁ -N = NG ₁₁ -R ₁₃ -Z ₁₁ R ₁₁ -N = A group capable of splitting an N group from G ₁₁ , specifically, OH, SH or NHR ₁₄ (R ₁₄ is a hydrogen atom, an alkyl group, an aryl group, -COR ₁₅ , or- SO ₂ R ₁₅ and R
₁₅ is a hydrogen atom, an alkyl group, an aryl group, and heterocyclic group), it may be a functional group which reacts directly with G _11, such as COOH, (wherein, OH, SH, NHR _14, - COO
H may be temporarily protected to generate these groups by hydrolysis of an alkali or the like) or (R ₁₆ and R ₁₇ are a hydrogen atom, an alkyl group, an alkenyl group,
Or it may be a functional group which becomes capable of reacting with the G ₁₁ by reacting a nucleophile such as hydroxide ions and sulfite ions as an aryl group or a heterocyclic group).

The ring formed by G ₁₁ , R ₁₃ and Z ₁₁ is preferably a 5- or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are the compounds represented by the general formulas (b) and (c).

General formula (b) In the formula, Rb ^{1 to} Rb ⁴ are a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), and an aryl group (preferably having 6 carbon atoms).
To 12) and may be the same or different.
B is an atom necessary for completing a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1,
(N + m) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
A cyclohexene ring, a cyclopentene ring, a benzene ring, an aphthalene ring, a pyridine ring, a quinoline ring and the like.

Z ₁₁ has the same meaning as in formula (a).

General formula (c) In the formula, Rc ¹ and Rc ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or the like, and may be the same or different. Rc ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p represents 0, 1 or 2. q represents 1-4. Rc ¹ , Rc ² and
Rc ³ may be bonded to each other to form a ring as long as Z ₁₁ can perform intramolecular nucleophilic attack on G ₁₁ .

Rc ¹ and Rc ² are preferably a hydrogen atom, a halogen atom, or an alkyl group, and Rc ³ is preferably an alkyl group or an aryl group.

q preferably represents 1-3, and when q is 1, p is 1
Or 2; when q is 2, p represents 0 or 1; when q is 3, p represents 0 or 1; when q is 2 or 3, a plurality of (CRc ¹ Rc ² ) are the same or different. Is also good.

Z ₁₁ has the same meaning as in formula (a).

A ₁₁ and A _{12 each} represent a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably, the sum of the substituent constants of a phenylsulfonyl group or a Hammet is -0.1.
A phenylsulfonyl group substituted to be 5 or more), 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 is -0.5 or more; or Straight-chain, branched or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic groups). A ₁₁ and A ₁₂ are most preferably hydrogen atoms.

R ₁₁ or R _{12 in} the general formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups and the like.
Examples of the polymer include those described in JP-A No. 1-100530.

R ₁₁ or R _{12 in} the general formula (I) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups and the like U.S. Pat.Nos. 4,385,108, 4,459,347, JP-A-59-195,233, JP-A-59-200,231 and JP-A-59-200,231. -201,045, same
59-201,046, 59-201,047, 59-201,048, 59
-201,049, JP-A-61-170,733, JP-A-61-270,744,
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501, No. 62-6
The groups described in 7,510 are exemplified.

Specific examples of the compound represented by the general formula (I) are shown below. However, the present invention is not limited to the following compounds.

As the nucleating agent hydrazine compound used in the present invention, in addition to those described above, RESEARCH DISCLOSURE I tem 23
516 (November 1983, p. 346) and references cited therein, as well as U.S. Patent Nos. 4,080,207, 4,269,929, and 4,27.
6,364, 4,278,748, 4,385,108, 4,459,347
No. 4,560,638, No. 4,478,928, UK Patent 2,011,39
1B, JP-A-60-179,734, JP-A-62-270,948, JP-A-63-29,75
No. 1, 61-170,733, 61-270,744, 62-270,948
No., EP217,310, EP356,898, US4,686,167, JP-A-62-178,246, 63-32,538, 63-104,047, 6
3-121,838, 63-129,337, 63-223,744, 63-
234,244, 63-234,245, 63-234,246, 63-29
No. 4,552, No. 63-306,438, JP-A No. 1-100,530, No. 1-10
No. 5,941, No. 1-105,943, JP-A-64-10,233, JP-A-1
-90,439, JP-A-1-276,128, 1-280,747, 1-2
No. 83,548, No. 1-283,549, No. 1-285,940, Japanese Patent Application No. 63-1
No. 47,339, No. 63-179,760, No. 63-229,163, Japanese Patent Application No. 1-
18,377, 1-18,378, 1-18,379, 1-15,755
Nos. 1-16,814, 1-40,792, 1-42,615, 1-
Nos. 42,616, 1-123,693 and 1-126,284 can be used.

The addition amount of the hydrazine compound as a nucleating agent in the present invention is from 1 × 10 ^-6 mol to 5 × per mol of silver halide.
It is preferably contained in an amount of 10 ⁻² mol, and particularly preferably in the range of 1 × 10 ⁻⁵ mol to 2 × 10 ⁻² mol.

As a method of dissolving and dispersing the hydrazine compound of the nucleating agent of the present invention, the same method as that of the redox compound can be employed.

The 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.

Configuration example 1). A silver halide emulsion layer containing the compound of the present invention and a protective layer are provided on a support. These emulsion layers or protective layers may contain a new hydrazine compound as a nucleating agent.

Configuration example 2). On a support, a first silver halide emulsion layer and a second silver halide emulsion layer are sequentially provided, and a nucleating agent is added to the first silver halide emulsion layer or an adjacent hydrophilic colloid layer. Containing a new hydrazine compound as the second
The compound of the present invention is contained in a silver halide emulsion layer or an adjacent hydrophilic colloid layer.

Configuration example 3). In the configuration example 2), the order of the two emulsion layers is reversed.

In 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.

Configuration example 4). A silver halide emulsion layer containing a new hydrazine compound as a nucleating agent on a support, and on the emulsion layer or between the support and the silver halide emulsion layer,
It has a hydrophilic colloid layer containing the compound of the present invention.

 A particularly preferred configuration is Configuration Example 2) or 3).

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly 0.5 μm.
The following is preferred. Although there is basically no limitation on the particle size distribution, monodispersion is preferred. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic and octahedral, and irregular such as spherical and tabular.
It may be one having a suitable crystal or one having a complex form of these crystal forms.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, and the like may coexist.

In the emulsion layer of the present invention, or other hydrophilic colloid layer,
A water-soluble dye may be contained as a filter dye or for various purposes such as prevention of irradiation.
As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the inherent sensitivity range of silver halide, and safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the range of 350 nm to 600 nm are used to increase the light absorption.

These dyes are added to the emulsion layer depending on the purpose,
Alternatively, it is preferable to add and fix a non-photosensitive hydrophilic colloid layer above the silver halide emulsion layer, that is, a non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with the mordant before use.

Different by the molar extinction coefficient of the dye, but usually 10 ^-2 g / m ² ~
It is added in the range of 1 g / m ² . Preferably 50mg~500mg / m ²
It is.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, some of which are as follows.

The dye is dissolved in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] for the non-photosensitive hydrophilic colloid layer of the present invention. It is added to the coating solution.

These dyes can be used in combination of two or more kinds.

The dye of the present invention is used in an amount necessary to enable handling in a bright room.

The amount of the specific dye is generally ^{10 -3 g / m 2 ~1g /} m 2,
In particular it is possible to find the preferred amount in the range of ^{10 -3 g / m 2 ~0.5g /} m 2.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sodium alginate;
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and various kinds of copolymers such as polyvinylpyrazole. Synthetic hydrophilic polymeric substances can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and iridium may be contained. An example is U.S. Pat.No. 2,448,060
And British Patent No. 618,061.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin.

As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindene) ), Pentaazaindenes; and many other compounds known as antifoggants or stabilizers, such as benzenethiosulfonate, benzenesulfonate, benzenesulfonamide, and the like. Rukoto can. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salt (chrom alum, etc.), aldehydes, glutaraldehyde, etc., N-methylol compound (dimethylol urea, etc.), dioxane derivative, active vinyl compound (1,3,5-triacryloyl-hexahydro-s) -Triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4
-Dichloro-6-hydroxy-s-triazine, etc.),
Mucohalogen acids and the like can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol ester, polyethylene glycol sorbitan ester, polyalkyl Nonionics such as glycolalkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars Surfactant; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group, or a phosphate group, such as alkyl phosphates; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or Amphoteric surfactants such as phosphates, alkyl betaines, and amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. Further, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

Examples of the development accelerator suitable for use in the present invention or the accelerator for nucleation and infectious development include JP-A-53-77616 and JP-A-54-3773.
In addition to the compounds disclosed in 2, 53-137, 133, 60-140, 340, and 60-14959, various compounds containing an N or S atom are effective.

 Next, specific examples are listed.

These accelerators have an optimal addition amount that varies depending on the type of the compound, but 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^−3.
It is desirable to use it in the range of 0.1 g / m ² . These accelerators are dissolved in a suitable solvent (H ₂ O), such as alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

 These additives may be used in combination of a plurality of types.

To obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or U.S. Pat.
It is not necessary to use a high alkali developer close to pH 13 described in JP-A-975, and a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains at least 0.10 mol / l of sulfite ion as a preservative, and has a pH of 9.0 to 1
With a developer having a pH of 2.3, particularly pH 10.5 to 12.0, a negative image with a sufficiently high contrast can be obtained.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and TH James describes "The Theory of the Photograp
hic Process ", 4th edition, published by Macmillan, pages 298 to 327, can be used.

For example, dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-
Pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol), ascorbic acid, hydroxylamines, and the like can be used alone or in combination. .

The silver halide light-sensitive material of the present invention particularly contains dihydroxybenzenes as a main developing agent and 3
-Suitable for processing with a developer containing pyrazolidones or aminophenols. Preferably in this developer dihydroxybenzenes 0.05 to 0.5 mol / l,
The 3-pyrazolidones or aminophenols are used in a range of not more than 0.06 mol / l.

Further, as described in U.S. Pat. No. 4,269,929, the development speed can be increased by adding amines to a developer to shorten the development time.

Other developers include pH buffers such as sulfites, carbonates, borates and phosphates of alkali metals, bromides,
It can contain a development inhibitor such as iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. Also, if necessary, a water softener, a dissolution aid, a color tone agent,
It may contain a development accelerator, a surfactant (especially preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, and a silver stain inhibitor (for example, 2-mercaptobenzimidazole sulfonic acids) of the film.

As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C.

Although it is preferable to use an automatic developing machine for photographic processing, according to the method of the present invention, even if the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is set to 90 seconds to 120 seconds. Thus, a photographic characteristic of a negative tone with a sufficiently high contrast can be obtained.

JP-A-56-24, as a silver stain inhibitor in the developer of the present invention,
The compound described in No. 347 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Further pH used for developer
As the buffer, compounds described in JP-A-60-93,433 or compounds described in JP-A-62-186259 can be used.

When the light-sensitive material of the present invention is a color light-sensitive material, at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer is provided on the support. The number and order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, even if the above-mentioned arrangement order is reversed, the arrangement order is obtained such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer, JP-A-61-43748, JP-A-59-113438,
No. 59-113440, No. 61-20037, couplers as described in the specification of No. 61-20038, and may contain a DIR compound, etc., and contain a color mixing inhibitor as usually used. Is also good.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of high-speed emulsion layer and low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62-20
As described in JP-A Nos. 0350, 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in Japanese Patent Publication No. 55-34932,
From the farthest side from the support, blue light-sensitive layers / GH / RH / GL / RL can be arranged in this order. JP-A-56-25738, 62
As described in -63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the lower-sensitivity silver halide emulsion layer having a lower sensitivity, and the lower layer is more than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, a medium-speed emulsion layer /
They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four or more layers, the arrangement may be changed as described above.

No. 4,663,271 to improve color reproduction
No. 4,705,744, 4,707,436, JP-A-62-160
A toner layer (CL) with a multilayer effect that has a different spectral sensitivity distribution from the main photosensitive layer such as BL, GL, and RL described in the specifications of JP-A Nos. 448 and 63-89850 is disposed adjacent to or close to the main photosensitive layer. Is preferred.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, a preferable silver halide contained in the photographic emulsion layer is silver iodobromide, iodobromide containing about 30 mol% or less of silver iodide. It is silver chloride or silver iodochlorobromide. Particularly preferred is from about 2 mol% to about 25 mol%
Silver iodobromide or silver iodochlorobromide containing up to silver iodide.

When the photographic material of the present invention is a color photographic paper,
As the silver halide contained in the photographic emulsion layer, those composed of silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used. Here, the phrase "contains substantially no silver iodide" means that the silver iodide content is 1 mol%.
Or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride emulsion can be used. Although this ratio can take a wide range depending on the purpose, the silver chloride ratio is 2 mol%.
Those described above can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used as a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%, more preferably at least 95 mol%. For the purpose of reducing the replenishment amount of the developing solution, an emulsion of substantially pure silver chloride having a silver chloride content of 98 to 99.9 mol% is also preferably used.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparatio
n and types) ”, and No. 18716 (November 1979), 64
8, Grafkid, "Physics and Chemistry of Photography," published by Paul Montell (P. Glafkides, Chemie et Phisique Photograp
hique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi).
c Emulsion Chemistry (Focal Press, 1966)), "Production and coating of photographic emulsions" by Zekriman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photo).
graphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is not exposed during imagewise exposure to obtain a dye image,
It is preferable that the silver halide fine particles are not substantially developed in the developing process and are not fogged in advance.

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably 0.5 to 10 mol% of silver iodide
It contains.

The fine grain silver halide preferably has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
μm is more preferred.

Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,5
It is preferable to add a compound which can react with formaldehyde described in No. 03 and can be fixed to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 968, 4,314,023, 4,511,649, EP 249,473A, and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
No., Research Disclosure No.24230 (June 1984)
Mon), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730
No. 55-118034, No. 60-185951, U.S. Pat.
No. 630, No. 4,540,654, No. 4,556,630, International Publication W
Those described in, for example, No. 088/04795 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Those described in JP-A-61-42658 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Dec. No. 17643, VII-
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413, U.S. Pat.No. 4,004,929, U.S. Pat.
No. 146,368 are preferred. U.S. Patent No.
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,774,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120 as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
It is described in 2,137 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents described in the paragraph, JP-A-57-151944, 57-154234
And Nos. 60-184248, 63-37346 and 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A-59-157638 and JP-A-59-170840.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427 and the like, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP 60-18
No. 5950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A, 313,30
A coupler that releases a dye that recolors after detachment described in No. 8A,
RD Nos. 11449, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,555,477, and leuco dyes described in JP-B-63-75747 are released. Coupler, U.S. Patent No. 4,774,18
Couplers that emit the fluorescent dye described in No. 1 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylphenyl phosphate, etc.), benzoic esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-tert)
-Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl- 2-butoxy-5-ter
t-octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer to form a hydrophilic polymer. It can be emulsified and dispersed in a water-soluble colloid aqueous solution.

Preferably, International Publication No.W088 / 00723, twelfth
Homopolymers or copolymers described on pages 30 to 30 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

In the color light-sensitive material of the present invention, JP-A-63-257747
No. 62-272248, and JP-A-1-80941.
2-benzisothiazolin-3-one, n-butyl p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or fungicides such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color peppers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering by A. Green et al. (Photogr.
Sci. Eng.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a serometer (swelling meter) of the type described below.
T _1/2 is defined as 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds.
Defined as the time to reach 2.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is
150-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
The development can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, chlorides, bromides,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity Granting agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And their salts can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.

That is, The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III) such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate
I) Acetate is preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
Nos. 53-72623, 53-95630, 53-95631, 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group described in, for example, July, 1983; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832,
Nos. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, 2,748,430
No. 45-883
Polyamine compound described in No. 6; Other JP-A-49-40,943
Nos. 49-59,644, 53-94,927, 54-35,727,
Compounds described in JP-A Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,2
Compounds described in JP-A-90,812 and JP-A-53-95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
And acetic acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP-A-294769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring,
JP-A-62-183460 describes a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, JP-A-62-183461, a method of increasing a stirring effect by using a rotating means, There are a method of moving the photosensitive material while bringing the emulsion surface in contact with the provided wiper blade to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in
It is preferable to have the photosensitive material conveying means described in JP-A-191257, JP-A-60-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath.
The effect of preventing performance deterioration of the processing liquid is high. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated atrium isocyanurate, and other benzotriazoles. (19
1986) Sankyo Publishing, Sanitary Technology Society, “Sterilization and sterilization of microorganisms,
A fungicide described in "Encyclopedia of Fungicides" (1986), "Encyclopedia of Fungicides and Antifungal Agents" (1986) edited by the Industrial Technology Association and the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and aqueous time can also be variously set depending on the characteristics of the light-sensitive material, applications, etc., but are generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Publication No.
-8543, 58-14834, and 60-220345 can all be used.

Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and metals described in U.S. Pat.No.3,719,492 Salt complexes and urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

The compound of the present invention can be used for a photothermographic material. Regarding photothermographic materials, U.S. Pat.
No. 4,474,867, No. 4,478,927, No. 4,507,38
No. 4, No. 4,500,626, No. 4,483,914, JP-A-58-14
9046, 58-149047, 59-152440, 59-154445
No., 59-165054, 59-180548, 59-168439,
59-174832, 59-174833, 59-174834, 59-
174835, 61-232451, 62-65038, 62-253159
No. 63-316848, No. 64-13546, European Patent Publication 210,6
Nos. 60A2 and 220,746A2.

The photothermographic material basically has a photosensitive silver halide, a binder, a dye-donating compound, and a reducing agent (a dye-donating substance may also serve as a reducing agent) on a support, Further, an organic silver salt and other additives can be contained as required.

The photothermographic material may be one that gives a negative image upon exposure or one that gives a positive image. The method of giving a positive image is a method using a direct positive emulsion (a method using a nucleating agent or a light fogging method) as a silver halide emulsion, and a dye that emits a positive diffusible dye image. Any of the methods using a donor compound can be adopted.

There are various methods for transferring a diffusible dye, for example, a method of transferring to a dye fixing layer with an image forming solvent such as water, a method of transferring to a dye fixing layer with a high boiling organic solvent, and a method of transferring to a dye fixing layer with a hydrophilic heat solvent. A method of transferring, a method of transferring to a dye-fixing layer having a dye-receptive polymer by utilizing thermal diffusivity or sublimability of a diffusible dye has been proposed,
Any of them may be used.

Further, as the image forming solvent, for example, there is water,
This water is not limited to so-called pure water, but includes water in a widely and customarily used sense. Also, pure water and methanol, DMF,
A mixed solvent with a low boiling point solvent such as acetone and diisobutyl ketone may be used. Further, a solution containing an image formation accelerator, an antifoggant, a development terminator, a hydrophilic heat solvent, and the like may be used.

(Example 1) (First photosensitive emulsion layer) 0.13 M silver nitrate aqueous solution, (NH ₄ ) ₃ PhCl ₆ corresponding to 1 × 10 ⁻⁷ mol per mol of silver, and 2 × 10 ⁻⁷ mol of K ₃ IrCl
₆ Double-jet the halogen salt aqueous solution containing 0.04 M apotassium bromide and 0.09 M sodium chloride into sodium chloride and gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinthione at 38 ° C. for 12 minutes with stirring. Method, the average grain size is 0.15 μm, and the silver chloride content is 70.
Nucleation was performed by obtaining mol% silver chlorobromide grains. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution and a halogen salt aqueous solution containing 0.26 M potassium bromide and 0.65 M sodium chloride were added by a double jet method over 20 minutes. Thereafter, 1 × 10 ^-3 mol of KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, added with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5, and further, thiosulfuric acid was added per mol of silver. 5 mg of sodium and 8 mg of chloroauric acid were added, heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl 1,3,3a was used as a stabilizer.
150 mg of 7-tetrazaindene was added. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%). These emulsions were divided and used as sensitizing dyes in an amount of 1.times.10.sup.- ³ mol of 5- [3- (4-sulfobutyl) -5-chloro-2 per mol of silver.
-Oxazolidylidene] -1-hydroxyethyl-3-
(2-pyridyl) -2-thiohydantoin was added, and 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 5 × 10 ⁻⁴ mol of a short-wave cyanine dye represented by the following structural formula (a), The polymer represented by (b) (200 m
g / m ² ) and a dispersion of polyethyl acrylate (200 mg / m ²
m ² ) 1,3-Divinylsulfonyl-2-propanol (200 mg / m ² ) as a hardener and the following nucleating agent hydrazine compound (c) were added.

(Coating of Intermediate Layer) Gelatin 1.0 g / m ² Hardener (c) 4.0 wt% to gelatin (Second photosensitive emulsion layer) Preparation of photosensitive emulsion B 4 × / mol of silver was added to an aqueous gelatin solution kept at 50 ° C. 10 ^-7
An aqueous silver nitrate solution and an aqueous solution of potassium iodide and potassium bromide were added simultaneously over 60 minutes in the presence of moles of potassium iridium (III) chloride and ammonia, and the pAg between them was kept at 7.8 to obtain an average particle size of 0.28 μm. A cubic monodispersed emulsion having an average silver iodide content of 0.3 mol% was prepared. The emulsion was desalted by flocculation, and then 40 g of inert gelatin per mole of silver was added.
5,5'-dichloro-9-ethyl- as sensitizing dye
3,3'-Bis (3-sulfopropyl) oxacarbocyanine and a KI solution of 10 ^-3 mol per mol of silver were added, and the mixture was aged for 15 minutes and then cooled.

Coating of the second photosensitive emulsion layer The photosensitive emulsion B was redissolved, and the following reagents were added at 40 ° C. so that the coated silver amount was 0.4 g / m ² and the gelatin was 0.5 g / m ^2. did.

5-methylbenzotriazole 5.0 × 10 ⁻³ mol / Ag mol 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene 2 × 10 ⁻³ mol / Ag mol Polyethyl acrylate 30 wt% vs. gelatin hardening Agent (c) 4.0 wt% vs. gelatin Redox compound of the present invention or comparative example shown in Table 1 2.0
× 10 ⁻⁵ mol / m ² (coating of protective layer) As a protective layer, gelatin 1.5 g / m ² and polymethyl methacrylate particles (average particle size 2.5 μ) 0.3 g / m ² were added to the following surfactant It was applied using.

Surfactant These samples were exposed to tungsten light at 3200 ° K through an optical wedge and a contact screen (Fujifilm, 150L chain dot type), and then exposed to the following developer A at 34 ° C.
It was developed for 30 seconds, fixed, washed with water and dried.

 The halftone was expressed by the following equation.

* Half tone = exposure amount that gives 95% halftone dot area ratio (logE95%-exposure amount that gives halftone dot area ratio of 5% (logE5%)) The halftone dot quality was visually evaluated on a five-point scale. In the evaluation, "5" indicates the best quality and "1" indicates the worst quality.
"5" and "4" are practically usable as the halftone dot masters for plate making, "3" is a practically usable limit level, "2",
"1" is a quality that cannot be used.

As can be seen from the results in Table 1, Comparative Sample 1-f and all the samples of the present invention exhibited a wide halftone and high dot quality. Example 2. (Preparation of photosensitive emulsion B) 5.0 × 10 per mol of silver in gelatin solution
After simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , gelatin is added after removing soluble salts by a method well known to those skilled in the art, and 6-methyl-4 as stabilizer without aging
-Hydroxy-1,3,3a, 7-tetrazaindene was added. This emulsion was a cubic monodispersed emulsion having an average size of 0.15 μm.

(Coating of Photosensitive Emulsion Layer) The nucleating agent hydrazine compound I-8 (75 g /
m ² ), 5-methylbenzotriazole (5 × 10 ⁻³ mol / Ag
mol), polyethyl acrylate latex (30 wt% vs. gelatin), and 1,3-divinylsulfonyl-2-propanol (2.0 wt% vs. gelatin). The application amount was 3.5 g / m ² .

Second layer Gelatin (1.0 g / m ² ) Third layer To photosensitive emulsion B, 5-methylbenzotriazole (5 ×
10 ^-3 mol / Agmol), polyethyl acrylate latex (30 wt% vs. gelatin), 1,3-divinylsulfonyl-2
-Propanol (2 wt% to gelatin) and the redox compound of the present invention shown in Table 2 were added, and the coated silver amount was
It was applied so as to be 0.4 g / m ² .

Fourth layer (protective layer) Gelatin 1.5 g / m ² , polymethyl methacrylate particles (average particle size 3.5 μ) 50 mg / m ² as a matting agent, and the following surfactants and stabilizers as coating aids: And a protective layer containing a UV absorbing dye was applied and dried.

The sample was exposed to an image as shown in FIG. 1 through a document as shown in FIG. 1, developed at 38.degree. C. for 20 seconds, fixed, washed with water, dried, and then printed to obtain the image quality of the printed characters. An evaluation was performed.

Character extraction quality 5 means that a 30 μm wide character is reproduced when an appropriate exposure is performed so that a halftone dot area of 50% becomes 50% halftone dot area on a return photosensitive material using an original as shown in FIG. The image quality is very good and the image quality is very good. On the other hand, the extracted character image quality 1 is an image quality that can reproduce only characters having a width of 150 μm or more when the same appropriate exposure is given. Rank was set. Three or more is a practical level.

The results are shown in Table 2. The sample of the present invention is excellent in the character extraction image quality.

[Brief description of the drawings]

FIG. 1 shows a configuration at the time of exposure in the case where a character extraction image is formed by overlapping, and the reference numerals indicate the following. (B) Transparent or translucent paste base (b) Line drawing original (black part shows line drawing) (c) Transparent or translucent paste base (d) Halftone original (black part is halftone dot (E) Returning photosensitive material (note that the hatched portion indicates the photosensitive layer)

Continuation of the front page (56) References JP-A-64-72140 (JP, A) JP-A-64-72139 (JP, A) JP-A-63-296032 (JP, A) JP-A-2-93484 (JP) , A) JP-A-2-93487 (JP, A)

Claims (5)

(57) [Claims] Claims: 1. A redox compound having at least one silver halide photographic emulsion and capable of releasing a nucleation development inhibitor by being oxidized to the photographic emulsion layer or another hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising: However, the nucleation development inhibitor, as a substituent or a part of the substituent, a nitroso group, (R ₃₁ represents a hydrogen atom or a halogen atom), quinones,
Fused pyridines, pyrazines, tetrazoliums,
It has amine oxides, azoxy compounds, and coordination compounds having oxidizing ability, and does not have a nitro group, an anion group, or a non-ring-fused pyridine group as a partial structure. 2. The halogen according to claim 1, wherein the redox compound has, as a redox group, hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones. Silver halide photographic material. 3. The silver halide photographic material according to claim 1, wherein the redox compound has a hydrazine as a redox group. 4. A redox compound represented by the following general formula (R-1):
A silver halide photographic material, which is at least one of the compounds represented by formulas (A) to (R-3). General formula (R-1) General formula (R-2) General formula (R-3) In these formulas, R ₁ represents an aliphatic group or an aromatic group. Represents G ₂ is a mere bond, -O-, -S- or And R ₂ represents a hydrogen atom or R ₁ . 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 synonymous with A ₁ or Represents A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R _1. Time represents a divalent linking group, and t represents 0 or 1. PUG includes, as a substituent or part of a substituent, a nitroso group, (R ₃₁ represents a hydrogen atom or a halogen atom), quinones,
Fused pyridines, pyrazines, tetrazoliums,
It represents a nucleating development inhibitor having an amine oxide, an azoxy compound, and a coordination compound having an oxidizing ability. However, it does not have a nitro group, an anion group, or an unfused pyridine group as a partial structure. 5. The silver halide photographic light-sensitive material according to claim 1, further comprising a compound represented by the following general formula (I). General formula (I) In the formula, R ₁₁ represents an aliphatic group or an aromatic group, and R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group. Represents a thiocarbonyl group or an iminomethylene group. A ₁₁ and A ₁₂ both represent 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.