JPH04136838A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain good dot picture quality high in contrast and sensitivity by incorporating a redox compound to be allowed to release a nucleus-forming development inhibitor by being oxidized in a photographic emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:This photographic sensitive material has at least one of the silver halide emulsion layers or another hydrophilic colloidal layer containing the redox compound to be allowed to release the nucleus-forming development inhibitor by being oxidized. This inhibitor contains no nitro, anion, nor pyridine group, and it is preferred that the redox compound has hydroquinones, pyrocatechols or hydrazines as the redox group, or it is a kind of compound represented by one of the formulae I - III.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it provides a negative image with high contrast and high sensitivity, and a good halftone image quality. This invention relates to silver halide photographic materials.

(Prior Art) A group of compounds that can release photographically useful groups through a redox reaction have been known.

Recent examples include JP 61-213847, JP 61-278852, JP 62-296゜138, JP 61-66641, JP 64-88451, and U.S. Pat. No. 4,684,604. Examples include compounds described in .

As described in the above patents, the compounds known so far can be used for various purposes depending on the type of photographically useful group.

For example, in the field of silver halide photographic materials for photolithography, in order to deal with the variety and complexity of printed matter, there are many types of photographic materials that have good original reproducibility, stable processing solutions, and replenishers. There are requests for simplification, etc.

Particularly in the line drawing process, manuscripts are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction.

On the other hand, enlarging (stretching) or reducing (shrinking) net photographs is widely used in the making of catalogs and large posters.
In plate making that uses enlarged halftone dots, the number of lines becomes coarser, resulting in blurred dots. When reduced, the number of lines per inch is larger than that of the original, and a thinner point is photographed. Therefore, in order to maintain halftone reproducibility, an image forming method having a wider latitude is required.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain sensitivity to these light sources, photographic materials are usually orthosensitized. However, it has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of lenses, and as a result, image quality tends to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

As a system that meets the demands for a wide latitude, a lithium-type silver halide photosensitive material made of silver chlorobromide (with a silver chloride content of at least 50%) is developed with an extremely low effective concentration of sulfite ions (usually 0.1%). mole/1 or less)
A method is known in which a line image or a halftone dot image with high contrast and high black density, in which image areas and non-image areas are clearly distinguished, is obtained by processing with a hydroquinone developer. However, due to the low concentration of sulfite in the developing solution, this method is extremely unstable to air oxidation, and various efforts and innovations have been made to keep the solution activity stable. Currently, the process is extremely slow, reducing work efficiency.

For this reason, we have created an image forming system that eliminates the instability of image formation caused by the above-mentioned development method (lithographic development system), develops with a processing solution that has good storage stability, and provides ultra-high contrast photographic characteristics. One of these is US Pat. No. 4,166.742, US Pat. No. 4,168,977, and US Pat. No. 4. 221. No. 857, No. 4,224,401,
No. 4,243°739, No. 4,272,606, and No. 4,311.781, surface latent image type silver halide photographic light-sensitive materials containing a specific acylhydrazine compound are prepared at pH 11. , 0 to 12.3, contains a sulfite preservative of 0.15 mol/1 or more, and is processed with a developer having good storage stability to form an ultra-high contrast negative image with γ of over 10. was suggested. This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide, which has a high silver chloride content. There is.

The above image system has sharp halftone dot quality, processing stability,
There is a need for a system that exhibits superior performance in terms of speed and original reproducibility, or has even improved original reproducibility in order to cope with the variety of modern printed materials.

For example, attempts to improve image quality include
A method is known in which a development inhibitor is released from a redox compound having a carbonyl group in the manner of a silver image, as disclosed in Japanese Patent No. 3847. However, even when these compounds are used, the extension of halftone gradation is insufficient.

Therefore, it has been desired to develop a photosensitive material that can form a high-contrast halftone image using a stable developer and that can be broadly controlled in image tone.

On the other hand, efforts have been made to improve work efficiency in the printing and reversing processes by performing the work in a brighter environment, and for this reason, it is necessary to work in an environment that can essentially be called a bright room. Progress has been made in the development of photosensitive materials for plate making and exposure printers.

The photosensitive material for bright room use described in this patent refers to a photosensitive material that can safely use light having a wavelength of 400 nm or more, which does not contain an ultraviolet component, as safelight light for a long period of time.

The photosensitive material for bright room use used in the collection and reversing processes uses a developed film on which characters or halftone images have been formed as an original, and the original and the photosensitive material for reversing are exposed in close contact to form a negative image/image. It is a photosensitive material used to perform positive image conversion or positive image/positive image conversion. It is desired to have the ability to perform positive image conversion ■ It is desired to have the ability to adjust the tone of halftone images and the line width of character line images, and photosensitive materials for bright room reversal that meet these requirements have been provided. Ta.

However, in the advanced image conversion work of forming cut-out character images by overlapping and turning, the conventional method using a bright room turning process using a light-sensitive material for bright rooms is not suitable for the conventional darkroom turning process using a conventional darkroom turning photosensitive material. The disadvantage of this method is that the quality of the extracted character image deteriorates compared to the method described above.

To explain in more detail the method of forming cut-out character images by overlapping, as shown in Fig. 1, transparent or translucent pasting bases (A) and (C) (polyethylene terephthalate usually having a thickness of about 100 μm) are used. (b) A film on which characters or line images are formed (line drawing original) (b) and a film on which a halftone dot image is formed (halftone original) (d).
The halftone dot original (D) is then exposed with the emulsion side of the return photosensitive material (E) brought into close contact with the halftone dot original (D).

After exposure, a development process is performed to form blank white portions of line drawings in the halftone image.

The important points in this method of forming a character image are:
Ideally, negative image/positive image conversion is performed according to the halftone dot area and image width of each halftone dot original and line drawing original. However, as is clear from Figure 1, halftone originals are exposed by being brought into direct contact with the emulsion surface of the photosensitive material for return, whereas line drawing originals are exposed using the pasting base (C) and the halftone original (C). (iv) The photosensitive material for return is exposed to light through the intermediate layer.

For this reason, if an exposure amount is given to faithfully convert a halftone original into a negative image/positive image, the line drawing original will be subjected to pin-poke exposure through the spacer of the pasting base (c) and the halftone original (d). The width of the drawing line for the blank white part becomes narrower. This is the cause of deterioration in the quality of the extracted character image.

Is there a system using hydrazine to solve the above problems?
No. 3-314541 and No. 61-13545, but these are not sufficient and further improvements are desired.

A method using a redox compound that releases a development inhibitor in a photolithography system using a hydrazine compound as a nucleating agent is disclosed in JP-A-56-153.336 and JP-A-153-61.
-213,847, 62296.138, 64-
72,139, 64-12,140, etc. are known. Various development inhibitors have been described as development inhibitors for these redox compounds, but nucleating development inhibitors that are effective in nucleating development systems using nucleating agents include:
There is no suggestion as to which development inhibitor is particularly effective in inhibiting the nucleating development system.

Nitro groups, anionic groups,
Although redox compounds that release development inhibitors containing pyridine groups in their partial structure have been described, they do not necessarily provide a sufficiently effective inhibitory effect in nucleating development systems.

Nucleation and infection development is carried out using the Fuji Film GRANDBX system (Fuji Photo Film ■ or Kodak Ultratec).
System (Eastman Kodak Co., Ltd.)
This is a new development chemistry used in the image forming method of Lid, ). This development chemistry is explained in "Journal of Photographic Society of Japan" Vol. 52, No. 5, pp. 390-394 (1989) and "Journal of Photographic Science" Vol. 35, p. 162 (1987). Nucleating active species are generated through the development process of silver halide grains with a normal developing agent and the resulting cross-oxidation between the oxidation product of the developing agent and the nucleating agent. It consists of two processes: exposure, nucleation and contagion development of weakly exposed silver halide grains.

Therefore, since the entire development process consists of the sum of the normal development process and the nucleation development process, as a development inhibitor,
In addition to the conventional development inhibitors known in the art, compounds that inhibit the nucleation-contagious development process may exert an inhibitory effect. The latter are referred to herein as nucleating development inhibitors.

OBJECTS OF THE INVENTION A first object of the present invention is to provide a novel redox compound that releases a nucleation development inhibitor that is effective in nucleation development systems.

A second object of the present invention is to provide a novel redox compound which has excellent storage stability and which rapidly releases a nucleating development inhibitor.

The third object of the present invention is to have a wide exposure latitude in line drawing photography, ultra-high contrast (especially γ value of 10 or more),
An object of the present invention is to provide a photographic material having high resolution.

A fourth object of the present invention is to provide an ultra-high contrast photographic material that can reproduce line drawings well and has a high backclarant density (Dmax).

A fifth object of the present invention is to have a wide exposure latitude and high density in halftone image photography, and to have clear outlines of halftone dots.
An object of the present invention is to provide a photographic material with uniform shape and excellent halftone dot quality and ultra-high contrast.

(Structure of the Invention) The various aspects of the present invention have been achieved by a silver halide photographic light-sensitive material characterized by containing a dox compound capable of releasing a nucleating development inhibitor upon oxidation.

The redox compound of the present invention which can release a nucleating development inhibitor when oxidized will be explained.

The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones, and more preferably hydroxyl groups.

The hydrazines used as the redox compound capable of releasing a nucleating development inhibitor upon oxidation of the present invention are preferably of the following general formula (R-]), general formula R-2)
, represented by general formula (R-3). General formula (R-1)
Particularly preferred are compounds represented by:

General formula (R-1,) RIN N Gj(T+me)t PUGA
, A2 General formula (R-2) R1-G2-cl-N-N-CH2Cl-(Time)
A, A, A,.

PUG General Formula (R-3) In these formulas, R1 represents an aliphatic group or an aromatic group. G1 represents a 10- group, a -C-C- group, or a -P- group. G2 represents a simple bond, 2-R2 O--S- or -N=, R2 represents the same group as R or a hydrogen atom, and if multiple R2s exist in the molecule, they are the same. There may or may not be one.

A, , A2 represents a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In general formula (R-1), at least one of AA2 is a hydrogen atom. A3 is synonymous with A, or -CH2
CH(Time) represents -PUGA4.

A4 is a nitro group, a cyano group, a carboxyl group, a sulfo group, or -G, -G, -R, (in this case, the two -G and -G2-R in the molecule may be the same or different. good.

).

Time represents a divalent linking group, and t represents 0 or I. PUG stands for nucleating development 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 anionic group refers to those described in Japanese Patent Application No. 2-64,717, such as a sulfo group and a carboxy group.

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

In general formulas (1;'-1), (R-2), and (R-3), the aliphatic group represented by R1 preferably has 1 to 3 carbon atoms.
In particular, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

This alkyl group may have a substituent.

In general formulas (R-1), (R-2), (R-3),
The aromatic group represented by R1 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.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, and an isoquinoline ring. Among these, those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amine group, Ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, nor\rogen atom, cyan group, sulfo group, aryloxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Examples include carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, etc. Preferred substituents include linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), aralkyl group (preferably has 7 to 30 carbon atoms), alkoxy group (preferably has 1 to 30 carbon atoms), substituted amino group (preferably has 1 to 30 carbon atoms)
~30 alkyl group substituted), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms)
, a ureido group (preferably one having 1 to 40 carbon atoms,
Examples include phosphoric acid amide groups (preferably those having 1 to 40 carbon atoms).

G in general formulas (R-1), (R-2), (R-3)
1 is preferably a -C- group or a -5O2- group, -〇-
Most preferred are groups.

A,,A2 is preferably a hydrogen atom, and A3 is a hydrogen atom, -CH2-CH (PU GA under Timd).

is preferred.

In general formulas (R-1), (R-2), and (R-3), T
ime represents a divalent linking group and may have a timing adjustment function.

The divalent linking group represented by Time represents a group that causes Time-PUG released from the oxidized product of the redox mother nucleus to release PUG through one or two subsequent steps of reaction.

As the divalent linking group represented by Time, for example, U.S. Pat.
30) and 4. 358. Those that release PUG by an intramolecular ring-opening reaction after ring cleavage as described in US Pat. No. 4,330.617, US Pat. No. 4,446,
No. 216, No. 4゜483.919, JP-A No. 1983-1.
U.S. Pat. No. 4,409,323, which releases PUG with the production of acid anhydride through the intramolecular ring-closing reaction of the carboxyl group of succinic acid monoester or its analogs, as described in U.S. Pat. 4,421゜845, Research Disclosure Magazine No. 21.228
(December 1981), U.S. Patent No. 4.416,97
No. 7, (Unexamined Japanese Patent Publication No. 57i35,944), Unexamined Japanese Patent Publication No. 58-
209,736, No. 58-209,738, etc., by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group to generate quinomonomethane or an analog thereof and release PUG. U.S. Patent No. 4,420,554
0), JP-A-57-135,945, JP-A No. 57-18
No. 8,035, No. 58-98,728 and No. 513
- Releases PUG from the γ position of the enamine by electron transfer of the enamine structure-containing moiety of the nitrogen-containing heterocycle as described in No. 209,737, etc.; A device that releases PUG through an intramolecular ring-closing reaction of an okyne group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of the telo ring, US Patent No. 4.14
No. 6,396 (Unexamined Japanese Patent Publication No. 52-90932)
9-93,442, JP-A-59-75475, JP-A-60-249148, JP-A-60-2491.49
JP-A-51-146,828 and JP-A-57-1, which release PUG with the formation of aldehydes as described in
．． Nos. 79,842 and 59-1.04,641 which release PUG with decarboxylation of the carboxyl group; -0-C0OCR,,R,,-PUG(R,,,R
,.

represents a -valent group. ), which releases PUG with decarboxylation and subsequent generation of aldehydes;
JP-A-60-7,429 which releases PUG with the production of isocyanate, U.S. Patent No. 4,43
Examples include those that release PUG through a coupling reaction with an oxidized form of a color developer, as described in No. 8,193.

Tim of general formula (R-1), (R-2), (R-3')
The divalent group represented by e is preferably represented by the following general formula (T
-1) is represented by the general formula (T-6). In these, ** represents the site where Time binds to PUG, and * represents the other binding site.

General formula (T-], ) In the formula, W represents an oxygen atom, a sulfur atom or a -N group, R21 and R22 represent a hydrogen atom or a substituent, R23 represents a substituent, and t is 1 or R or Represents 2. When t is 2, two -W-CR2□ represent the same thing or different things. When R21 and R2□ represent a substituent, representative examples of R23 are R2 group, R24CO- group, R2,502- group,
Examples include R,, NGO- group or R2"h R2, NSO2- group. Here, R2t represents an aliphatic group, aromatic group, or heterocyclic group, and R2S represents an aliphatic group, aromatic group, or heterocyclic group. Represents a group or a hydrogen atom.

Each of R21, R2□ and R2h represents a divalent group,
It also includes the case where they are connected to form a cyclic structure.

Specific examples of the group represented by general formula (T-1) include the following groups.

NH302C,H.

General formula (T-2) *-Nu-L Jnk-E-** Formula where Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, and E represents an electrophilic group, It is a group that can cleave the bond with the mark ** upon receiving a nucleophilic attack from Nu, and L
i n k represents a linking group that sterically associates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by general formula (T-2) are as follows.

In the general formula, W, R2,, R22 and t have the same meaning as explained for (T-1). Specifically, the following groups may be mentioned.

29= NH30,CH3 CH2-** General formula (T-4) General formula (T-5) *-0-C-** *-5-C-** General formula (T-6) In the formula, W and R21 have the same meaning as explained in general formula (T-1). Specific examples of the group represented by general formula (T-6) include the following groups.

Also, as Time, general formula (T-1) ~ -general formula T-
A group formed by combining two or more groups represented by 6) is also useful. Preferred specific examples thereof are shown below. ＊、＊
* has the same meaning as in general formulas (T-1) to -general formula T-6).

*-0-CH2 0-C CH.

Hh *-0-(,-Ni CH2k N C**H3 0CH30 II I II *-0-C-O-(CH2 drow N-C-**These Tim
For specific examples of the divalent linking group represented by e, see JP-A-61-236,549 and JP-A-64-88451.
It is also described in detail in Japanese Patent Application No. 63-98.803, etc.

PUG represents a group having a nucleation development inhibitory effect as (TTime'+TPUG or PUG.The nucleation development inhibitor represented by PUG has a heteroatom, is bonded via a heteroatom, and has a substituent A nitroso group, -N-halogen R as part of a group or substituent.

groups (represents a halogen bromine atom, chlorine atom, etc., R3 represents a hydrogen atom or a halogen atom), quinones (e.g., benzoquinone, naphthoquinone, quinone monoimine, quinone diimine, etc.), ring-fused pyridines (e.g., quinoline, phenanthroline, acridine, etc.), pyrazines (e.g., quinoxaline, phenazine, etc.), tetrazoliums, amine oxides (e.g., pyridine oxide, etc.), azoxy compounds, coordination compounds with oxidizing ability (e.g. , Fe chelate compound, etc.).

The group represented by PUG is preferably represented by the general formula (P-1
) or represented by general formula (P-2).

General formula (P-1) It is a group having the same definition as R in .

X2 is an aliphatic group, an aromatic group, or these groups and -O
S Se NR3] CR33 is R32
It is a divalent group formed by combining -c--5o--so2 (same definition as ), and may be substituted. Preferred substituents include the same as those listed as the substituent for R1 in general formula (R-1). X3 is a nitroso group, an N-halogen group, a quinone group, a condensed pyridine, a pyrazine, a tetrazolium, an amine oxide, an azoxy compound, a coordination compound having oxidizing ability, etc. as mentioned above as a substituent of PUG. and may be further substituted. As preferred substituents, the same ones as those listed as the substituent for R1 in general formula (R1) can be mentioned. m is 1, but X3 is a quinone, a condensed pyridine, a pyrazine,
When representing tetrazoliums, amine oxides, azoxy compounds, or coordination compounds having oxidizing ability, it may be 0.

General formula (P-2) In the formula, X2. X has the same definition as general formula (P-1),
X4 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle together with the nitrogen atom. n represents 0 or 1.

The nitrogen-containing heterocycle is preferably a heteroaromatic ring.

Furthermore, these heteroaromatic rings are preferably 5- to 6-membered rings,
It may be a monocyclic ring, a condensed ring, or a substituted ring. Representative examples of preferred heteroaromatic rings include:
For example, pyrrole, imidazole, pyrazole, l, 2.
3-triazole, 1.2.4- triazole, tetrazole, 2-thioxathiazoline, 2-oxathiazoline, 2-thioxaoxazoline, 2-oxaoxazoline, 2-thioximidacillin, 2-oxaimidacillin, 3- Thioxa-1,2,4-triazoline, 3-oxa-1,2,4-1-riazoline, 1, 2-oxazoline-5-thione, l, 2-thiazoline-5-thione, 1,2-oxazoline 5 -one, l, 2-thiazolin-5-one, 2-thioxa-1,3,4-thiadiazolin, 2-oxa-1,3,4-thiadiazolin, 2
-thioxa-1,3,4-oxadiazoline, 2-oxa1, 3. 4-Oxadiazoline, 2-thioxadihydropyridine, 2-oxadihydropyridine, 4-thioxadihydropyridine, 4-oxadihydropyridine, isoindole, indole, indazole, henctriazole, benzimidazole, 2-thioxabenzimidazole, 2oxa Benzimidazole, benzoxazoline 2-thione, asaindenes, penzoxazoline-2-one, benzothiazoline-2-thione,
Benzothiazolin-2-one, carbazole, purine,
carboline, phenoxazine, phenothiazine, pyrazolopyridines of various ring-fused positions, pyrazolopyrimidines, pyrazolopyrroles, pyrazolopyrazoles, pyrazoloimidazoles, pyrazolooxazoles, pyrazolothiazoles, pyrazolo Examples include triazoles, imidazolopyridines, imidazolopyrimidines, imidazolopyrroles, imidazoloimidazoles, imidazolooxazoles, imidazolothiazoles, imidazolotriazoles, and the like.

More preferred heteroaromatic rings include, for example, pyrrole, imidazole, pyrazole, triazole, tetrazole, 2-thioxathiazoline, 2-thioxaoxazoline, indole, indazole, benzotriazole, benzimidazole, 2thioxa-1,3,4-thiadiazole , azaindene, 5-thioxa-tetrazoline,
Examples include 2-thioxa-1,3,4-oxadiazoline, 3-thioxa-1,2,4-triazoline, pyrazolopyridines of various condensed ring positions, pyrazoloimidazole, etc., and particularly preferred are pyrazole, It is a heteroaromatic ring containing a pyrazole skeleton, such as indazole and pyrazolopyridine.

These heterocyclic compounds may have a substituent. Examples of substituents include mercapto group, hydroxy group, alkyl group, aralkyl group, nearkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, and sulfamoyl group. group, carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, halogen atom, ano group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carphonamide group, sulfonamide group,
Examples include phosphonamide groups.

Also, in the formulas (R, -1), (R-2), and (R-3), R or -(-T im e→=PUG is
Among them are ballast groups commonly used in immobile photographic additives such as couplers, and general formulas (R-1) and (R-2).
, (R-3) may be incorporated with a group that promotes the adsorption of the compound represented by (R-3) onto silver halide.

The ballast group has the general formula (R-]), (R-2), (R-3
) is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the formula from diffusing into other layers or into the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, and an amide group. group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidacyline-2-thione, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, 1. 2. 4-triazoline-3-thione, l, 3. 4-oxazoline-2-thione, benzimidacillin-2-thione,
Cyclic thioamide groups, linear thioamide groups, aliphatic mercapto groups, aromatic mercapto groups, such as henzoxazoline-2-thione, penzothiazoline-2-thione, thiotriazine, l,3-imidacillin-2-thione, Petero ring mercapto group (if the carbon atom to which the -8H group is bonded is a nitrogen atom, it has the same meaning as a cyclic thioamide group which has a tautomeric relationship with this group, and specific examples of this group are those listed above) ) a group having a disulfide bond,
Pentutriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, pentuthiazole, thiazole, thiazoline, pentuoxazole, oxazole, oxazoline, thiasiasol,
Examples include 5- to 6-membered nitrogen-containing heterocyclic groups consisting of a combination of nitrogen, oxygen, sulfur, and carbon such as oxathiazole, triazine, and azaindene, and heterocyclic quaternary salts such as benzimidazolinium. .

These may be further substituted with a suitable substituent.

Examples of the substituent include those mentioned above as the substituent for R1.

Specific examples of the compounds used in the present invention are listed below, but the present invention is not limited thereto.

CH2NC C,,H,.

CN O The synthesis of the redox compound used in the present invention is described in, for example, JP-A No. 61-213,847, No. 62260.153, and U.S. Pat. 684. No. 604, patent application 1986-
No. 98,803, U.S. Patent No. 3,379,529, U.S. Pat. No. 3,620,746, U.S. Pat.
, No. 332,878, JP-A-49-129,536,
It can be synthesized according to the synthesis method described in Japanese Patent No. 56-153.336, Japanese Patent No. 56-153,342, and the like.

The compound of general formula (R-1) of the present invention can generally be synthesized by the route shown below. That is, the corresponding 2 equivalents of P
It is synthesized by reacting + -H with trichloromethyl chlorocarbonate in an organic solvent such as THF in the presence of a base such as triethylamine to form a symmetrical carbonyl compound, and then reacting it with the corresponding hydrazine compound. (synthesis route 1), or after condensation of the corresponding P U GffT im e+, H with -p-1 trophenyl CIO carbonate in the presence of a base, the corresponding redox compound of the present invention can be synthesized with silver halide 1 It is used within the range of lXl0-' to 5 x 10-2 mol, more preferably 1 x 10'''5 to 1 x 10-2 mol per mole.

The redox compound of the present invention can be used in a suitable water-miscible organic solvent, such as alcohols (methanol, ethanol, propatool, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used by dissolving it in

In addition, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, chryceryl triacetate, or diethyl phthalate can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified. A dispersion can also be prepared and used.

Alternatively, by a method known as solid dispersion method,
The powder of the redox compound can also be dispersed in water using a ball mill, a colloid mill, or an ultrasonic wave.

In the sensitive material of the present invention, it is preferable to use a hydrazine derivative as a nucleating agent.

Nucleating agents preferably used in the present invention include hydrazine derivatives represented by the following formula (I).

General formula (I) R,, -N　-N-G,, -R,,.

A,, A,.

In the formula, R11 represents an aliphatic group or an aromatic group, and R1
2 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, and G represents a -C- group, -5O2-
group, -3O- group, -PR3□I] group, -c-c- group, thiocarbonyl group, or iminomethylene group, A 11% A and 12 are both hydrogen atoms, or one of them is substituted with a hydrogen atom and the other is substituted with a hydrogen atom. or represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In general formula (I), the aliphatic group represented by R1+ preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
~20 straight chain, branched or cyclic alkyl groups. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carphonamide group.

The aromatic group represented by R11 in 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. Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidasyl ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a hendithiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R11 is an aryl group.

The aryl group or unsaturated heterocyclic group of R11 may be substituted, and typical substituents include 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, 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, diacylamide group, imide group, R,, -N HCN C- group, etc. Preferred substituents include linear, branched or cyclic alkyl groups (preferably those having 1 to 20 carbon atoms), aralkyl groups (preferably those having 1 to 3 carbon atoms in the alkyl part)
monocyclic or bicyclic), alkoxy groups (preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably has 2 to 30 carbon atoms)
, sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms), etc. .

The alkyl group represented by R1 in general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, such as a halogen atom, a hydroxyl group, a cyano group, a carboxyne group, a sulfo group, an alkoxy group, a phenyl group, Substituents such as alkyl or arylsulfonyl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfamoyl groups, nitro groups, heteroaromatic ring groups, R,, -N -N-G, - groups have 1
1A12 may be present, and these groups may also be substituted.

The aryl group is preferably a monocyclic or bicyclic aryl group, such as one containing a benzene ring. This aryl group is, for example, a halogen atom, an alkyl group, a cyano group,
It may be substituted with a carboxyl group, a sulfo group, a sulfonyl group, etc.

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 monocyclic, and the substituent includes a halogen atom.

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
An alkylamino group or an arylamino group is preferred, and may be substituted with an alkyl group, a halokene atom, a cyano group, a nitro group, a carboxyne group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 0 carbon atoms, or an arylcarbamoyl group, which 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 or an aryloxycarbonyl group having 1 to 10 carbon atoms, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R12, preferred are those in which G is -C
- group, hydrogen atom, alkyl group (e.g., methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0 −
hydroxybenzyl group, etc.), aryl groups (e.g., phenyl group, 3,5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), and especially hydrogen Atoms are preferred.

In addition, when G l is a -3O2 group, R3
For example, a phenyl group, etc.) or a substituted amino group (for example, a dimethylamino group, etc.) are preferred.

When G l l is a -3O- group, R82 is preferably a cyanobenzyl group, a methylthiobenzyl group, etc., a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, a phenyl group are preferable, and a phenoxy group is particularly preferable. .

When G l l is an N-substituted or unsubstituted imino methylene group, R+2 is preferably a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R12, the substituents listed for R11 can be applied.

G l in general formula (I) is most preferably a -C- group.

Also, R1° splits the G11R12 portion from the remaining molecule, -G, -R,. It may be one that causes a cyclization reaction to produce a cyclic structure containing atoms of the moiety, and specifically, one that can be represented by general formula (a).

General formula (a) 1h Z In the formula, Zll attacks G l 1 nucleophilically, and Gz
It is a group that can split the R13Z11 moiety from the remaining molecules, and R+3 is R1□ with one hydrogen atom removed, and Zl
l makes a nucleophilic attack on G l l, G1 R13, Zl
A cyclic structure can be generated with l.

More specifically, Z l 1 easily undergoes a nucleophilic reaction with G when the hydrazine compound of general formula (I) generates the next reaction intermediate by oxidation etc. R,, -N=N-G ,, -R,3-Z R,, is a group that can split the -N=N group from Gll,
Specifically, OH, SH or NHR, (R, is a hydrogen atom, an alkyl group, an aryl group, -COR,, or -3O2R15, and R11 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group) It may be a functional group that directly reacts with G11, such as OH, SH, NHR, etc.), C0OR, etc. may be temporarily protected by N-R,, 0) or -C-R,, -(, -R,, (R,6,
R17 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group) by reacting with a nucleophile such as a hydroxide ion or a sulfite ion.
It may also be a functional group that is capable of reacting with.

Furthermore, the ring formed by G1□, Rli, and Zll is preferably a 5- or 6-membered ring.

- Among those represented by formula (a), preferred are those represented by general formulas (b) and (C).

General formula (b) fCRb'Rb'S;C-' 1 B In the formula, Rb'-Rb' represents a hydrogen atom, an alkyl group (preferably one having 1 to 12 carbon atoms), or an alkenyl group (preferably one having 1 to 12 carbon atoms). 2 to 12 carbon atoms), an aryl group (preferably one having 6 to 12 carbon atoms), and may be the same or different. B is an atom necessary to complete a 5-membered ring or 6-membered ring that may have a substituent, m and n are 0 or 1
and (n+m) is 1 or 2.

Examples of the 5- or 6-membered ring formed by B include a cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

Zll has the same meaning as general formula (a).

General formula (c) C3iNte7CRc'Rc'f-; In formula 2, R
c', Re2 is a hydrogen atom, an alkyl group, an alkenyl group,
They represent an aryl group or a halogen atom, and may be the same or different. Re3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p is 0 or 1
represents. q represents 1-4. Rc', Re2 and Re3 may be bonded to each other to form a ring as long as the structure allows intramolecular nucleophilic attack to Z(j or Gll).

Rc' and Re2 are preferably hydrogen atoms, halogen atoms,
or an alkyl group, and Re3 is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is 1, p represents 1 or 2; when q is 2, p represents 0 or 1; when q is 3, p represents 0 or l; Or, in the case of 3, a plurality of (CRc'Rc'') may be the same or different.

Zll has the same meaning as general formula (a).

A l l, A12 is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a sum of Hammett's substituent constants of 10, 5
A benzoyl group substituted as above, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonamide F group, a carbonamide group, a hydroxyl group, Examples include carboxy group and sulfonic acid group.)) A1
2 is most preferably a hydrogen atom.

R11 or R12 of the general formula (I) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

Examples of the polymer include those described in JP-A-1-100530.

R11 or R1□ in general formula (I) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
U.S. Pat. No. 4,385.108, U.S. Pat.
No. 59,347, JP-A No. 59-195.233, No. 5
9-200゜231, same 5! J-201,045,
No. 59201.046, No. 59-201,047,
No. 59-201,048, No. 59-201,049, JP-A-61-170,733, No. 61270.74
No. 4, No. 62-948, Japanese Patent Application No. 62-67.508, No. 62-67.501, and No. 62-67.510.

Specific examples of the compound represented by general formula (I) are shown below.

However, the present invention is not limited to the following compounds.

I-4 ■ ■ ■ ■-13 ■ ■ (triC,H ■ H ■-22 ■-24 ■ ■ ■-25 ■■ Nucleating agent hydrazine compounds used in the present invention include:
In addition to the above, RESEARCHDISCLO5I
In addition to JRBItem 23516 (November 1983, P, 346) and the documents cited therein, U.S. Pat.
No. 4,276.364, No. 4278.748, No. 4,385,108, No. 4.459,347, No. 4
, No. 560,638, No. 4,478,928, British Patent No. 2,011°391B, Japanese Patent Application Publication No. 179,734/1986
No. 62-270,948, No. 6129.751, No. 61-170,733, No. 61-270,744
No. 62-270,948, EP 217°310, EP 356,898, US 4,686.167,
JP-A-62-178,246, JP-A No. 6L-32,538
No. 63-104,047, No. 63-12L 8
No. 38, No. 63-129.337, No. 63-223,
No. 744, No. 63-234, 244, No. 61-234
, No. 245, No. 63234.246, No. 63-294
No. ゜552, No. 63-306,438, JP-A No. 110
No. 0.530, No. 1-105,941, No. 1-105
, No. 943, JP-A-64-10,233, JP-A-1-
No. 90,439, JP-A No. 1276.128, 1-2
No. 80,747, No. 1-283,548, No. 1-28
No. 3,549, No. 1-285.940, Patent Application No. 1983-
147゜339, 63-179,760, 63
No. 229.163, Japanese Patent Application No. 1-18,377, 1-
No. 18,378, 1. -18,379, 1-15
, No. 755, No. 1-16,814, No. 1. -40,7
92, No. 1-42,615, No. 1-42,616, No. 1-123,693, and No. 1-126.284 can be used.

The amount of the nucleating hydrazine compound added in the present invention is from 1X10-' mol to 5 mol per mol of silver halide.
It is preferable to contain ×10 −2 mol, especially 1 × 1 O
The preferred addition amount is in the range of -5 mol to 2X10-2 mol.

As a method for dissolving and dispersing the nucleating agent hydrazine compound of the present invention, the same method as for the redox compound described above can be adopted.

The compounds of the invention are added to silver halide emulsion layers or other hydrophilic colloid layers. Further, it may be added to at least one of a plurality of silver halide emulsion layers.

Although some configuration examples will be given, the present invention is not limited to these.

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

Structure example 2), having a first silver halide emulsion layer and a second silver halide emulsion layer in this order on a support, the first silver halide emulsion layer or an adjacent hydrophilic colloid layer. A new hydrazine compound is contained as a nucleating agent, and the compound of the present invention is contained in the second silver halide emulsion layer or the adjacent hydrophilic colloid layer.

In Structure Example 3) and Structure Example 2), the order of the two emulsion layers is reversed.

In configuration examples 2) and 3), an intermediate layer containing gelatin or a synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the two photosensitive emulsion layers.

Structure example 4) has a silver halide emulsion layer containing a new hydrazine compound as a nucleating agent on a support, and a silver halide emulsion layer containing a new hydrazine compound as a nucleating agent is provided 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 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 iodochlorobromide, and silver iodochlorobromide.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
It is preferably 5μ or less. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse herein means that at least 95% of the particles by weight or number of particles is composed of particles having a size within ±40% of the average particle size.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubic or octahedral (or irregular crystal structures such as spherical or plate-like).
ular) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Two or more silver halide emulsions formed separately may be used in combination.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a chlorine salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. are allowed to coexist in the silver halide grain formation or physical formation process. You can.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. The filter dye may be a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a very thick spectral absorption in the inherent sensitivity range of silver halide, or a dye for safelight source when handled as a bright room photosensitive material. In order to increase the safety ak, a dye having a photogenic light absorption mainly in the region of Jj Onm-100 nm is used.

These dyes are added to the emulsion layer depending on the purpose, or they are added together with a mordant to the upper part of the silver halide emulsion layer, that is, to the non-light-sensitive hydrophilic colloid layer which is further away from the silver halide emulsion layer with respect to the support. It is preferable to use it by fixing it.

Although it varies depending on the molar extinction coefficient of the dye, it is usually 10-2 or 7.
m2~/? It is added in an area of 7 m2. Preferably Ir1jOmy~f007I1g/+112terol.

Specific examples of dyes include patent application Sho A/-JO? It is described in detail in the ltF issue, but some of them are listed below in SC2.

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

Two or more of these dyes can also be used in combination.

The dyes of the present invention are used in amounts necessary to permit full bright room handling.

The specific amount of dye used is generally 102/m2-7f
? /m, particularly in the range 10 7 /m - 0°397 m 2 .

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin conductors, graft polymers of gelatin and other polymers, aluminum/
, protein such as casein; hydroxyethyl cellulose,
Carboxymethyl cellulose, cellulose derivatives such as cellulose sulfate esters, sugar derivatives such as alginate, starch derivatives, polyvinyl alcohol? A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol partial acetal, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidasole, polyvinyl pyrazole, etc. can be used.

In addition to lime-treated gelatin, acid-treated gelatin may be used as the gelatin, and gelatin hydrolysates and gelatin enzymatically decomposed products may also be used.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem even if all complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium, are contained. A specific example is U.S. Patent 2, 4t<tl
, OAO'iEQ is described in British Patent No. 27♂, Ot1, etc.

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

As a reduction sensitizer, ld, stannous salt, amines, formamidine sulfinic acid, silanated compound, etc. can be used.

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

The photosensitive material of the present invention has the ability to prevent capri during the manufacturing process, storage, or photographic processing of the photosensitive material, or to improve its photographic performance.
For the purpose of stabilization, various chemical compounds can be included. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzotheanols, mercazototeadiazoles, aminotriazoles, and pentuteanol. mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (with guhydroquino substitution (/1313a) ,7)
Tetrazaindenes), grasshopper azaindenes, etc.: Many compounds known as antifoggants or stabilizers can be added, such as benzenetheosulfuric acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. . Preferred among these are benzotriazoles (eg !-methyl-benzotriazole) and nitroindazoles (eg !-nitroindazole). However, these compounds may be included in the processing solution.

The photographic light-sensitive material of the present invention may contain an organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium monoxide, etc.), aldehydes, geltal aldehyde, etc., N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (/, 3.J'-triacryloyl, etc.), xahydro-s-to'J7dine, /13-vinylsulfonyl 2-propatol, etc.), active rogen compounds (,2,gudichloro-2-hydroxy-3-)riazine, etc.), muco-Rogge/acids, These can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the photosensitive dye made using the present invention may include coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, sensitization, etc. For example, saponin (steroid type), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl) ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or polyethylene oxide adducts of polyalkylene glycol, glycol derivatives (e.g. acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyalcohols,
Nonionic surfactants such as alkyl esters of sugars;
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpholi Carbohydrates such as oxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates
Anio/surfactants containing acidic groups such as sulfo groups, phospho groups, sulfo ester groups, phosphate ester groups; amino acid groups, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl carboxylic acids, amines Amphoteric surfactants such as oxides; alkylamine salts,
Aliphatic or aromatic 1st. t, class ammonium salts,
Cationic surfactants such as heterocyclic ψ-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts B containing aliphatic or heterocycles can be used.

In particular, the surfactant preferably used in the present invention has a molecular weight A described in Japanese Patent Publication No. Sho JJ'-9117.2.
More than DO! Realkylene oxides. Additionally, for dimensional stability, a polymer latex such as polyalkyl acrylate may be included.

Development accelerators or nucleation infection promoters suitable for use in the present invention include JP-A No. 3-77 Alt and JP-A No. 3-77 Alt; -37732, 33-/37/33, AO-
/ lIO, 3410, same 10-, / <7ri351
Various compounds containing one N or S atom of the compounds disclosed in ', etc. are effective.

Next, specific examples will be listed.

The optimum amount of these accelerators to be added varies depending on the type of compound, but it is desirable to use them in the range of 1.0XIO-' to 0.5g/m, preferably 5.0X10-3 to O, 1g/7m. These promoters are dissolved in a suitable solvent (H2O, alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

A plurality of types of these additives may be used in combination.

In order to obtain ultra-high contrast photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer with a pH close to 13 as described in No. 9,975, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.10 mol/f1 or more of sulfite ion as a preservative, and p
Sufficient ultra-high contrast negative images can be obtained with a developer having a pH of 9.0 to 12.3, particularly a pH of 10.5 to 12.0.

There are no particular limitations on the developing agent that can be used in the method of the present invention, and there are no particular limitations on the developing agent used in the method of the present invention.
ryof the Photographic Pro
cessJ, 4th edition, published by Macmi11an, 29
Various compounds described on pages 8 to 327 can be used.

For example, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-3-pyrazolidone),
(p-aminophenol), ascorbic acid, hydroxylamines, etc. can be used alone or in combination.

In particular, the silver halide light-sensitive material of the present invention contains dihydroquinbenzenes as a main developing agent and 3-3 as an auxiliary developing agent.
Suitable for processing with developers containing pyrazolidones or aminophenols. Preferably, in this developer, dihydroxybenzenes are used in an amount of 0.05 to 0.5 mol/1.3-pyrazolidones or aminophenols in a range of 0.06 mol/l or less.

Further, as described in US Pat. No. 4,269,929, the development speed can be increased and the development time can be shortened by adding amines to the developer.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). I can do it.

If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (for example, 2-mercaptobenzimidazole sulfonic acids, etc.).

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thionanate, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

The processing temperature in the method of the invention is usually from 18°C to 50°C.
Selected between C.

Although it is preferable to use an automatic processor for photographic processing, the method of the present invention allows the total processing time from the time the photosensitive material is placed in the automatic processor to the time it comes out to be 90 to 120 seconds. , sufficiently ultra-high contrast negative gradation photographic characteristics can be obtained.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. Patent application 1986-109 as a solubilizing agent added to the developer.
Compounds described in No. 743 can be used. Furthermore, as a pH buffering agent for use in developing solutions, JP-A-60-93,4
Compounds described in No. 33 or JP-A-62-18625
Compounds described in No. 9 can be used.

It is sufficient that at least one silver halide emulsion layer of a green-sensitive layer and a red-sensitive layer is provided, and there are no particular restrictions on the number and order of the silver halide emulsion layer and the non-photosensitive layer.

A typical example is a silver halide photographic material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the photosensitive layer is generally a unit photosensitive layer. A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. but,
Depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be 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 between the uppermost layer and the lowermost layer.

For cough intermediate layer, JP-A-61-43748, JP-A-59-1
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (B11) / high sensitivity green sensitive layer (GW) / low sensitivity green sensitive layer (GL) /
High sensitivity red photosensitive layer (R
L) or [1+1/BL/GL/Gll/RH
/RL order, or B II / B L / G I
/ GL / RL / RII, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of R11/GL/RL. Furthermore, as described in JP-A Nos. 56-25738 and 62-63936, the blue-sensitive materials may be arranged in the order of Ji/GL/RL/G'll/R1+ from the side farthest from the support. You can also do it.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when composed of 3N having different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, the layers may be arranged in the following order: low-temperature emulsion layer/medium-sensitivity emulsion layer/high-sensitivity emulsion layer.

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

To improve color reproduction, U.S. Patent No. 4.66327
No. 1, No. 4,705,744, No. 4,707,4
No. 36, JP-A-62-160448, JP-A No. 63-898
The multilayer effect donor layer (CL) described in the specification of No.
) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on 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, preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodo, containing about 30 mol% or less of silver iodide. Silver chloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. It can be preferably used. Here, "substantially free of 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. This ratio can vary widely depending on the purpose, but the silver chloride ratio is 2 mol%.
The above can be preferably used. For light-sensitive materials suitable for rapid processing, so-called high silver chloride emulsions containing a high silver chloride content are preferably used. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more. For the purpose of reducing the amount of replenishment of the processing solution, a nearly pure chloride emulsion having a silver chloride content of 98 to 99.9 mol % is also preferably used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) N.

17643 (December 1978) pp. 122-23, “
■ Emulsion preparation
on and types)” and the same No.
18716 (November 1979), 648 pages, "Physics and Chemistry of Photography" by Glafkides, published by Paul Montell.
h1sique Photographique, P
aul MonLel+ 1967>, “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Du
ffinPhotographic Emulsion
Chemistry (Focal Press19
66)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
Published by Focal Press (V, L,, Zelikma
net al3Makingand Coating
Photographic [, mulsion, F
ocal Press, 1964).

U.S. Patent No. 3,574.628, U.S. Patent No. 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434,226, 4,414.310, 4,
433.048, 4,439,520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. Furthermore, it may be bonded with a compound other than silver halide, such as Rodan oxide or lead oxide. Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical μ) formation, chemical ripening and spectral sensitization. Additives used in such processes are subject to Research Disclosure No.
, 17643 and No. 18716, and the relevant parts are summarized in the table below.

In the present invention, it is preferred to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably 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 necessary. Preferably, it contains silver ash in an amount of 0.5 to 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, and preferably 0.01 to 0.5 μm.
02-0.2μ box is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, hendithiazolium-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 descriptions are shown in the table below.

Mulberry release old and 1? D17643 RD18716
1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer 25 pages 9 Hardeners 26 pages 651 pages 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same as above Patch agent Also, photographic performance improvement with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411,987 and US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No. 17643, ■-C-C.

Yellow couplers include, for example, U.S. Patent Section 3.93.
No. 3,501, No. 4,022,620, No. 1,
No. 326,024, No. 4,401,752, No. 4
, No. 248.961, Japanese Patent Publication No. 5B-1073'1, British Patent Box 1, No. 425, No. 020, No. 1,476.
No. 760, U.S. Pat.
Preferred are those described in No. 314,023, No. 4,511,649, European Patent No. 249, 473A, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent Section 4.31
No. 0,619, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3725.067, Research Disclosure No. 24220 (1984) June), Japanese Patent Application Publication No. 6
No. 0-33552, Research Disclosure No.
, 24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573
No. 0, No. 55418034, No. 60-1115951
No. 4,500.630, U.S. Pat. No. 4,540
．． Particularly preferred are those described in No. 654, No. 4, No. 556, No. 630, International Publication No. WO 38104795, and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Section 4,052,212.
No. 4,146.396, No. 4,228,23
No. 3, No. 4.296,200, No. 2,369.9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2,895.826, No. 3.772
．． No. 002, No. 3,758,308, No. 4.33
No. 4.011, No. 4.327.173, West German Patent Publication No. 3゜329.729, European Patent No. 121,365
No. A, No. 249453A, U.S. Patent Section 3,446,
No. 622, No. 4,333,999, No. 4,775
, No. 616, No. 4,451.559, No. 4,42
No. 7,767, No. 4.690.889, No. 4,2
No. 54212, No. 4.296.199, JP-A-61
-42658 etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure No.
No. 7-39413, U.S. Patent Section 4,004,929;
No. 4,138,258, British Patent Box 1,146.3
The one described in No. 68 is preferred. Also, U.S. Patent Section 4.
No. 774.181, a coupler that corrects unwanted absorption of a chromogenic dye by means of a fluorescent dye released upon coupling, or a coupler that can react with a developing agent to form a dye, as described in U.S. Patent No. 4.777.120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent Section 4.365.237 and British Patent Box 2,125.
．． Preferred are those described in No. 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4, 576910, British Patent No. 2.102.
It is described in No. 137, etc.

Couplers that release a photographically useful 'ti& upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD 176
43, patents described in sections ■ to F, JP-A-57-151
No. 944, No. 57-154234, No. 60-1842
No. 48, No. 63-37346, No. 63-37350, U.S. Patent No. 4,248.962, No. 4,782,01
The one described in No. 2 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Box No. 2.097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other compounds that can be used in the light-sensitive material of the present invention include the competitive couplers described in U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DI described in JP-A-6224252 etc.
R coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173302A
R,0, No. 11449, a coupler that releases a dye that recovers color after separation, as described in No. 313,308A.
No. 24241, bleach-promoting release coupler described in JP-A-61-201247, etc., U.S. Patent Section 4,555,47
Ligand releasing coupler described in No. 7 etc., JP-A-63-7
Couplers that release leuco dyes described in US Pat. No. 5,747, couplers that release fluorescent dyes described in US Pat. No. 4,774,181, and the like.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2.322.021 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-diamyl phenyl) phthalate, bis(2,4-diamyl phenyl) phthalate, (2,4-di-L-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or bosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexol phenyl phosphate, etc.), benzoic acid esters ( 2-ethylhexylbenzoate,
dodecylhensoate, 2-ethylhexyl-p-hydroxyhenzoate, etc.), amides (N,N-diethyldodecanamide, N,N diethyllaurylamide,
-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2+ 4-
tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline rust conductors (N, N-cyphtyl-2-butoxy-3-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylhenzene diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, a batter 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, Examples include cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. has been done.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in hydrophilic colloid water/8 liquid.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. 088100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl ρ-hydroxyhenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)henzimidazur.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643, and the same No. 187
16, page 647, right column to page 648, left column.

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, even more preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the membrane swelling rate TI/□ is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (
2 days), and the membrane swelling rate TI/□ can be measured according to methods known in the art. For example, Knee Green (eight, Green
) and others by Photographic Science Ant.
Engineering (Photogr, Sci, Eng,
), No. 194.2, pages 124-129, it can be measured by using a swellometer (swelling membrane) of the type described, and TI/□ is reached when treated with a color developer for 13 minutes and 15 seconds at 30°C. 90% of the maximum swelling film thickness is the saturated film thickness,
It is defined as the time required to reach the saturated film thickness of 172 mm.

The membrane swelling rate TI/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after wrapping. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, and No.
Development processing can be carried out by the usual method described in 615 left column to right column of No. 18716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline water solution containing a 100% aromatic primary amino color developing agent as a main component. Although p-
Phenyl diamine compounds are preferably used, typical examples of which include 3-methyl-4-amino-NN-diethylaniline, 3-methyl-4-amino-jl-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. Among cholera, especially 3-methyl-4-amino-N-ethyl-
Nβ-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain p11 buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, hengimidazoles, hendithiazoles or mercapto compounds. It generally contains a development inhibitor or an antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N and L biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic carriers such as diethylene glycol, development accelerators such as hensyl alcohol salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents. , aminopolycarboxylic acid, aminopolybosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxy Ethyliminodiacetic acid, ■-Hydroquinethylidene-1,
1-diphosphonic acid, nitrilo-N. Typical examples include N,N4rimethylenephosphonic acid, ethylenediamine-N,N,N,N tetramethylenephosphonic acid, ethylenediaminedi(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains 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 amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but -i is 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be lower than the precept. When reducing the replenishment amount, it is preferable to reduce the area of contact with the air in the processing tank to prevent evaporation of the liquid and air oxidation.

The contact area between the photographic processing solution and air in the processing tank can be expressed 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 for 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,
Method using a movable lid described in No. 033, JP-A-63
The slint development treatment method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. In addition, measures must be taken to suppress the accumulation of bromide ions in the developer.
It is also possible to lower the amount of replenishment by adjusting the number 1'.

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (1), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (I [ Aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (III) complexes, including ethylenediaminetetraacetic acid (I[1) complex salt and 1,3-diaminopropanetetraacetic acid (III) complex salt, are used from the viewpoint of rapid processing and environmental pollution prevention. preferred. In addition, iron aminopolycarboxylate (III
) Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. These aminopolycarboxylic acid iron (lI
[) The pH of bleach or bleach-fix solutions using complex salts is usually 4.
．． 0-8, but lower p for faster processing
It can also be processed with i(.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978), etc. Compounds containing mercapto i or disulfide groups, JP-A-1978 Thiazolidine derivatives described in Japanese Patent Publication No. 140129; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735, U.S. Patent No. 3,706.56
Thiourea derivatives described in No. 1; West German Patent No. 1,127,
No. 715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2.748,43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-40.943, No. 49-59,644, No. 53
-94,927, 54-35.727, 55-
Compounds described in No. 26,506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85
No. 8, West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-
Preference is given to the compounds described in No. 95.630. Further preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color S optical materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. A particularly preferred m-acid has an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and phosphonic acids to the fixer and clean fixer for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C2, preferably 35°C-45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460, and the method described in JP-A-62-183.
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, thereby increasing the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such an effect is particularly effective in shortening the processing time in each step and reducing the need for processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as free flow or down flow, and various other conditions. Can be set to . Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion PicLure and Te1evis
ion Engineers Volume 64, P, 248~
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems may be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, thiahendazole, chlorinated sodium isocyanurate, and other hensitriazole, etc., written by Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene “Microbial sterilization, sterilization, and anti-mildew technology J (1982), edited by Technical Society
Industrial Technology Association, Japan Antibacterial and Antifungal Science Venue “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).

The pl+ of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. 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 antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the grudge removal process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

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 processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 5B-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is between 33°C and 38°C, but higher temperatures can be used to accelerate the process and shorten the processing time! It is possible to improve the image quality and the stability of the processing solution by lowering the temperature for 1 hour or vice versa.

/ / The compound of the present invention can be used in heat-developable photosensitive materials.

Regarding heat-developable photosensitive materials, U.S. Patent No. 11.11A3
．． No. 079, No. F, g74t, a'J7, Shig Hiroshi,
t, t7F,? No. 27, No. t, t, ro7゜3♂O No., No. ≠, O00, A,? No. 1, Hiroshi No. 1.

Hiro♂3. RI/μ issue, Tokukai Shoyu f-/4' Ri Ogu Otsu issue, same! ? -/≠70≠7, same jter/Hahihiro O issue, same jter/! Gu Hirohiro J issue, same! Tar/OtsujOyo ≠ issue, same! Tarl♂Oj≠g No., same Tatar 76g≠3ri No., same Tatar/
7 Hiro r3λ, same evening/7μ, 33, same j'P-/7
4L♂34 No., Same Yota/7 Hiro♂3 Yo No., Same J/-2
32 Hiroj No. 1, same Otsu! -Otsu, t0.3r, same≦2-2
3rd/! No. 7, t3-3/Otsu g4tg, No. 2 Hiro-/
3 Tahiro No. 2, European Patent Publication No. 210, 1lOA 2, same,
220.

It is disclosed in No. 74tJA1 etc.

The above-mentioned heat-developable photosensitive material basically consists of photosensitive silver halide, a binder/der, a dye-providing compound, a reducing agent (
In some cases, the dye-donating substance also serves as a reducing agent), and if necessary, organic silver salts and other additives can be contained.

The above-mentioned heat-developable photosensitive material may be one that gives a 9-ga image upon exposure, or one that gives a positive image. Methods that produce positive images include a method that uses a direct visual emulsion (there are two types, a method that uses a nucleating agent and a method that uses light fogging) as a silver emulsion, and a method that uses a positive diffusive dye. Any system using an image-emitting dye-donating compound can be employed.

There are many ways to transfer diffusible dyes, such as transferring to a dye fixing layer using an image forming solvent such as water, transferring to a dye fixing layer using a high boiling point organic solvent, and transferring to a dye fixing layer using a hydrophilic thermal solvent. How to transfer, utilize the thermal diffusivity or sublimation of diffusible dyes to achieve dye receptivity? Two methods have been proposed in which the dye is transferred to a dye fixing layer containing a reamer, and any of these methods is acceptable.

Further, the image forming solvent includes, for example, water, and this water is not limited to so-called pure water, but includes water in the widely conventional sense. Still pure water and methanol, DM
A mixed solvent with a low boiling point solvent such as F, acetonate, or cyinobutyl ketone may be used. Furthermore, a solution containing an image formation accelerator, an anti-capri agent, a development stopper, a hydrophilic heat solvent, etc. may also be used. (Example I) (First photosensitive emulsion layer) A 0.13M silver nitrate aqueous solution , lXl0 per mole of silver
−' molar equivalent (NHI)l RI]Cρ.

and 2 x ] 0'' moles of 3 IrCp60.0
A halogen salt aqueous solution containing 4M potassium bromide and 0.09M sodium chloride was mixed with sulfur chloride and 1°3-
It was added to an aqueous solution of seratin containing trimethyl-2-imidasolidinethione by a double jet method at 38 °C for 12 minutes with stirring, and the average particle size was 0.15 μm.
Nucleation was performed by obtaining silver chlorobromide grains with a silver chloride content of 70 mol%.

Subsequently, in the same manner, 0.87M silver nitrate aqueous solution and 0°26M
of potassium bromide and a halogen salt aqueous solution containing 0.65M chloride+thorium were added over 20 minutes by a double jet method. Thereafter, conversion was carried out by adding 1×10-' mol of K I solution, washing with water using the flocculene conversion method according to a conventional method, and adding Seratin=I Og to pf (6,5, ■) 1.\g7.5 Further, 5 mg of sodium osulfate and 8 mg of chlorauric acid were added at 1:31 per mole of silver, and 6
The mixture was heated at 0° C. for 60 minutes to undergo chemical sensitization treatment, and 150 mg of 1,3.3a,7-titrasaindene was added as a stabilizer. The obtained particles had an average particle size of 0.28 μm1
They were silver chlorobromide cubic particles with a silver chloride content of 70 mol%.

(Coefficient of variation 10%).

These emulsions were divided to contain 1 x 10-3 mole of 5-[3-(4-sulfobutyl) per mole of silver as a sensitizing dye.
-5-chloro-2-oxasolicylidene]■-Hydroxyethyl-5-(2-pyridyl)2-thiohydantoin was added and an additional 2×10-” moles of 1-phenyl-5-
A dispersion of mercaptotetracil, 5XIO-'' moles of a short-wave cyanine dye represented by the following structural formula (a), a polymer represented by (b) (200 mg/m2) and polyethyl acrylate (200 mg/m2) as a hardening agent. 1
゜3-divinyl-sulfonyl-2-propatol (20
0mg/rn'), the following nucleating agent hydrazine compound (c
) was added.

Compound (a) Compound (1) (CI(2 CHsr, -(-CH2 CH:t 0 year old stone 1 OOH 00C2 0C (C-CH2→- Hydrazine compound (c) C2H.

CH.

2.8X10-”mol/m2 (coating of intermediate layer) Ceratin 1.0g7m hardener (
c) 4. Owt% wt% Chin (second photosensitive emulsion layer) Preparation of photosensitive emulsion B Add 4XlO per mole of silver to an aqueous solution of seratin kept at 50°C.
- In the presence of 7 moles of potassium iridium hexachloride (IIIJ) and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added over 60 minutes while p
By keeping Ag at 7.8, the average particle size is 0.2
A cubic monodisperse emulsion with a diameter of 8μ and an average silver iodide content of 0.3 mol % was prepared. This emulsion was desalted by the flocculation method, and then 40 g of inert gelatin per mole of silver was added and kept at 50°C as a sensitizing dye.5.
5'-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine was added to a K I solution of 10-1 mole per mole of silver, allowed to stand for 15 minutes, and then cooled. did.

Coating of the second photosensitive emulsion layer Photosensitive emulsion B was redissolved and the following reagents were added at 40°C, and the coating was applied so that the coating amount was 0.4 g/m and Seratin was 0.5 g/m. did.

5-Methylbenzyl liazole 5, OX]O-'moc/Agmo1 6-Methyl-4-hydroquino-1,3,3a.

7-chitrazaindene 2
c) 4. Shidox compounds of the present invention or comparative examples showing Owt% versus celadeceratin
2. OX 10-5mon/m (coating of protective layer) Seratin 1.5 g/m as a second protective layer
, polymethyl methacrylate-1 particles (average particle size 2.5μ
) 0.3 g/r& was applied using the following surfactants.

surfactant CH, C00CII H,.

CHCOOC, H.

37 mg/m SO+Na C,F, 7SO2NCH2C00K C3H+ 2.5 mg/m These samples were exposed to tungsten light at 3200° through an optical wedge and a contact screen (Fuji Film, 150L chain dot type) and then treated with developer A: 34°
It was developed for 30 seconds, fixed, washed with water, and dried.

The halftone gradation is expressed by the following formula.

* Exposure amount (βo
gE Exposure amount (po
gE5%) The halftone dot quality was visually evaluated on a five-level scale. The 5-level evaluation is
"5" indicates the best quality, and r I I indicates the worst quality.

As a halftone original plate for plate making, "5" and "4" are practical, "3" is the limit level of practical use, and "2" is of an impractical quality.

Comparative Compound B (Compound 2 described in JP-A-62-260°) As can be seen from the results in Table 1, Comparative Sample 1f and all the samples of the present invention had a wide halftone gradation and high halftone quality. Indicated.

Example 2゜(Preparation of Photosensitive Emulsion B) 5.0% per mole of silver was added to an aqueous solution of seratin kept at 50°C.
After simultaneously mixing a silver nitrate aqueous solution and a sodium chloride aqueous solution in the presence of XIO-' moles of (NH+) and R11Cβ6, gelatin was added after removing soluble salts and chemically ripened using methods well known in the art. 6-Methyl-4hydroxy-1,3,3a,7-chitrazaindene was added as a stabilizer without adding. This emulsion has an average size of 0
．． It was a monodisperse emulsion with a cubic crystal shape of 15μ.

(Coating of photosensitive emulsion layer) Nucleating agent hydrazine compound l-8 (75 g
/d), 5-methylbenzotriazole (5x 10
-3mon/Agmoβ), polyethyl acrylate latex (30wt% to gelatin), and 1,3-divinylsulfonyl-2-propatur (2,0wt% to seratin) were added.

The amount of silver coated was 3.5 g/m.

2nd layer Gelatin (], Og/m) 3rd layer Emulsion B, 5-methylbenztriazole (5X
l O'mol/AgmoA), polyethyl acrylate latex (30 wt% to gelatin), 3-divinylsulfonyl-2-propatur (2 wt% to seratin), and the redox compound of the present invention shown in Table 2. The coating was carried out so that the amount of silver coated was 0.4 g/m.

Fourth layer (protective layer) Gelatin 1. 5g/d, and 0.3g of polymethyl methacrylate particles (average particle size 2.5μ) as a matting agent.
/rrr', and a protective layer containing the following surfactant, stabilizer, and ultraviolet absorbing dye as coating aids was coated and dried.

surfactant CH2COOC6H.

C8F, 7SO2NCR,, C00K C, I-(.

2.5 mg/m stabilizer thioctic acid 2.1 mg/rn' UV absorber The image was exposed to light through an ultraviolet absorber, developed for 38° 020 seconds, fixed, washed with water, and dried, after which the cutout character image quality was evaluated.

Extracted character image quality 5 means that characters with a width of 30 μm are reproduced when a document as shown in Figure 1 is used and exposed appropriately so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return. In terms of image quality, the image quality is very good. -Emphatic character image quality 1
is an image quality that can only reproduce characters with a width of 150 μm or more when given the same appropriate exposure, and is considered poor character extraction quality, and is ranked between 5 and 1 with a sensory evaluation of 4 to 2. A score of 3 or higher is a practical level.

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

SO□N(C4H9)2 100mg/rn' A manuscript like the one shown in Figure 1 was printed on this sample using a Dainippon Screen (Co., Ltd. Meisho printer p-607).

[Brief explanation of drawings]

FIG. 1 shows the configuration at the time of exposure when forming a cut-out character image by overlapping and repeating, and each reference numeral indicates the following. (b) Transparent or semi-transparent pasting base (b) Line drawing original (black areas indicate line drawings) (c) Transparent or semi-transparent pasting base (d) Halftone dot original (black areas indicate halftone dots) Photosensitive material for printing (the shaded area indicates the photosensitive layer) Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment

Claims (1)

[Scope of Claims] 1) It has at least one silver halide photographic emulsion layer, and is capable of releasing a nucleating development inhibitor upon oxidation into the photographic emulsion layer or at least one other hydrophilic colloid layer. A silver halide photographic material containing a redox compound. However, the nucleating development inhibitor does not have a nitro group, an anion group, or a pyridine group as a partial structure. (2) Claim No. (1) characterized in that the redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrozines, hydroxylamines, and reductones as redox groups. The silver halide photographic material described in Section 1. (3) Claim (1) characterized in that the redox compound has a hydrazine as a redox group.
The silver halide photographic material described in Section 1. (4) The redox compound has the following general formula (R-1), (R
The silver halide photographic material according to claim (1), which is at least one compound selected from the compounds represented by -2) and (R-3). General formula (R-1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (R-2) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (R-3) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In these formulas, R_1 represents an aliphatic group or an aromatic group. G_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼group, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. There are tables, etc. ▼ Represents a group. G_2 is just a bond, -O-, -S-
or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, 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. General formula (
In R-1), at least one of A_1 and A_2 is a hydrogen atom. A_3 has the same meaning as A_1 or represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 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 represents a nucleating development inhibitor and does not contain a nitro group, an anion group, or a pyridine group as a partial structure. (5) The silver halide photographic material according to any one of claims (1) to (4), which contains a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_1 represents an aliphatic group or an aromatic group,
R_1_2 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, and G_1_1 has a ▲numeric formula, chemical formula, table, etc.▼ group, -SO_2- group, -
SO- group, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ group, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ group, represents a thiocarbonyl group or iminomethylene group, A_
1_1 and A_1_2 both represent a hydrogen atom, one hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.