JPH04267248A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To ameliorate picture quality and exposure latitude such as definition, graininess, dot quality, etc., of a silver halide photographic sensitive material. CONSTITUTION:This silver halide photographic sensitive material is made up by using a hydrazide compound, which is varied to a photographical effective compound or discharges a photographical effective reagent by an attack of a nucleophillic agent after being oxidized by an oxidative product of a developer and a compound with a dissociation radical of less than 7.5 in pKa value in combination.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to silver halide photographic light-sensitive materials, and in particular to compounds that can make photographically useful groups available in the development process, and methods for making full use of the properties of the compounds. This invention relates to a silver halide photographic material containing the compound.

0002

BACKGROUND OF THE INVENTION A group of compounds have been known that can release photographically useful groups through redox reactions. Recent examples include JP-A-61-213847, JP-A No. 61-278852 and US Pat. No. 4,684.
, No. 604. 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, in the plate making of catalogs and large posters, enlarging (stretching) or reducing (shrinking) halftone photographs is widely performed. will be photographed. 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, ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of the lens.
It has been found that the image quality tends to deteriorate as a result. Moreover, this deterioration is more noticeable for xenon lamp light sources. As a system that meets the demands for wide latitude, we use a lithium-type silver halide photosensitive material made of silver chlorobromide (silver chloride content of at least 50% or more) with an extremely low effective concentration of sulfite ions (usually 0.1 mol/min). A known method is to obtain a line or halftone image with high contrast and blackening density, in which image areas and non-image areas are clearly distinguished, 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.

[0004] For this reason, the instability of image formation caused by the above-mentioned development method (lithographic development system) can be resolved, and images can be developed with a processing solution having good storage stability to obtain ultra-high contrast photographic characteristics. There is a need for a forming system, one of which is U.S. Pat.
No. 77, No. 4,221,857, No. 4,224,40
No. 1, No. 4,243,739, No. 4,272,606
No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound was added was prepared at a pH of 11.0 to 12.3 and 0.00% of a sulfite preservative. A system has been proposed for forming ultra-high contrast negative images with γ of over 10 by processing with a developer containing 15 mol/l or more and having good storage stability. 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 shows excellent performance in terms of sharp halftone quality, rapid processing stability, and original reproducibility, but in order to cope with the diversity of printed materials in recent years, systems with improved original reproducibility have been developed. is desired.

As an attempt to improve image quality, 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, for example, JP-A-61-213847. 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 that can be used for printing. 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.

[0006] The photosensitive material for bright room use used in the plate collection and reversing processes uses a developed film on which characters or halftone images are formed as an original, and the original and the reversing photosensitive material are exposed in close contact. It is a photosensitive material used to perform negative image/positive image conversion or positive image/positive image conversion. A photosensitive material for bright room reversal is required to have the ability to perform negative image/positive image conversion. has been provided. However, in advanced image conversion work such as forming cut-out character images by overlapping,
The conventional method using a bright room reversing process using a light-sensitive material for bright rooms has the disadvantage that the quality of the cut-out character image deteriorates compared to the method using a dark room reversing process using a conventional reversing photosensitive material for dark rooms. there was. To explain in more detail the method of forming cut-out character images by overlapping, as shown in Figure 1 of JP-A-2-293736, transparent or translucent pasting bases (A) and (C) (usually (a polyethylene terephthalate film having a thickness of about 100 μm is used), a film on which characters or line images are formed (line drawing original) (b), and a film on which halftone dot images are formed (halftone original) (black). ) are superimposed to form an original, and the emulsion side of the return photosensitive material (e) is brought into close contact with the halftone original (d) for exposure.

[0007] After exposure, a development process is performed to form blank white portions of line drawings in the halftone image. An important point in such a method of forming a cut-out character image is that the negative image/positive image conversion should ideally be performed according to the halftone dot area and image width of each of the halftone dot original and the line drawing original. However, as is clear from Figure 1, halftone originals are exposed in direct contact with the emulsion surface of the photosensitive material for return, whereas line drawing originals are exposed using a pasting base (c) and a halftone original (black). ) is exposed to the photosensitive material for return through the intermediate layer. Therefore, if an exposure amount is given to faithfully convert the halftone image into a negative image/positive image, the line drawing original will be exposed out of focus through the spacer of the pasting base (c) and the halftone original (d). The line width of the blank white part of the line drawing becomes narrower. This is the cause of deterioration in the quality of the extracted character image. In order to solve the above problems, a system using hydrazine is disclosed in Japanese Patent Application Laid-open Nos. 62-80640 and 62-2359.
No. 38, No. 62-235939, No. 63-10404
No. 6, No. 63-103235, No. 63-296031
No. 63-314541, No. 64-13545,
However, it is not sufficient and further improvement is desired.

In color photographic materials, redox compounds that release development inhibitors exhibit effective performance for improving sharpness, graininess, and color reproducibility. However, in recent years, conventional compounds have been unsatisfactory in achieving increasingly sophisticated and wide-ranging improvements in photographic properties, and further improvements have been desired. That is, it is an undeniable fact that recently developed high-sensitivity color photographic materials sacrifice some sharpness and graininess in order to increase sensitivity. Furthermore, since the magnification of a disk-sized film is large during printing, graininess and sharpness are currently poor. Furthermore, materials that improve sharpness are desired for X-ray black and white photographic materials.

[0009]

[Problems to be Solved by the Invention] An object of the present invention is to provide a photographic material that has excellent image quality such as sharpness, graininess, resolution, and color reproducibility, has a wide exposure latitude, or has high sensitivity. be. The objects of the present invention are particularly in the field of silver halide photographic light-sensitive materials for photolithography, in which the exposure latitude in line drawing is wide and ultra-high contrast (in particular, the γ value is 1
0 or more) and has high resolving power, or has excellent halftone dot quality with wide exposure latitude and high density in halftone image shooting, clear outline of halftone dots, and uniform shape. The main object of the present invention is to provide a photographic material with ultra-high contrast.

0010

[Means for Solving the Problems] The objects of the present invention have been achieved by the following silver halide photographic material. That is, in a silver halide photographic material having at least one silver halide emulsion layer on a support, after the emulsion layer or other hydrophilic colloid layer is oxidized by an oxidation product of a developer, Hydrazide compounds that transform into photographically useful compounds or release photographically useful reagents upon attack by nucleophiles, and water-insoluble oils below neutrality that have a dissociative group with a pKa value of 7.5 or more. A silver halide photographic material characterized by containing a soluble compound.

The redox compound of the present invention having a hydrazine structure, the hydrazine portion of which is oxidized and converted into a photographically useful compound by a subsequent reaction, or which releases a photographically useful compound will be described. It has a hydrazine structure, and the hydrazine part is oxidized,
Examples of redox compounds that are transformed into photographically useful compounds by subsequent reactions include, for example, the following general formula (N-
1). General formula (N-1)

0012

[C4]

In the formula, R1 represents an aliphatic group or an aromatic group, and R2 represents a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxy group, aryloxy group, amino group or hydrazino group, G1 is -CO- group, -SO2 -
group, -SO- group, -P(O)(G2-R2)- group,
-COCO- group, thiocarbonyl group or iminomethylene group, G2 is a simple bond, -O- group, -S-
group, or -NR2- group. Both A1 and A2 represent a hydrogen atom, one of which is a hydrogen atom, and the other of which is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (N-1), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. It is. This alkyl group may have a substituent. The aromatic group represented by R1 in general formula (N-1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with an aryl group. Preferred as R1 is an aryl group, particularly preferably one containing a benzene ring.

The aliphatic group or aromatic group of R1 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, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, Alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide group, R2 -N
Examples include HCON(R2)CO- group (two R2's may be different), and preferred substituents include an alkyl group (preferably one with 1 to 20 carbon atoms) and an aralkyl group (preferably one with 7 to 20 carbon atoms). 30), 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 those having 2 to 20 carbon atoms), 3
0), sulfonamide group (preferably has 1 to 30 carbon atoms), ureido group (preferably has 1 to 30 carbon atoms), phosphoric acid amide group (preferably has 1 to 30 carbon atoms) things) etc. These groups may be further substituted.

The alkyl group represented by R2 in the general formula (N-1) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, benzene). (including rings)
. When G1 is a -CO- group, preferred among the groups represented by R2 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g. o
-hydroxybenzyl group, etc.), aryl group (e.g.,
(phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), and a hydrogen atom is particularly preferred. R2 may be substituted, and the substituents listed for R1 can be used as substituents. G1 in general formula (N-1) is most preferably a -CO- group.

[0017] Furthermore, R2 may be one that causes a cyclization reaction in which the G1 -R2 moiety is split from the residual molecule to produce a cyclic structure containing the atoms of the -G1 -R2 moiety; For example, JP-A-63-29
Examples include those described in No. 751. A1, A2
The most preferred is a hydrogen atom.

R1 or R2 in the general formula (N-1) 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, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Can be done. In addition, as a polymer, for example, JP-A-1-
Examples include those described in No. 100530.

R1 or R2 in general formula (N-1) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
No. 08, No. 4,459,347, JP-A-59-195
, No. 233, No. 59-200, No. 231, No. 59-20
No. 1,045, No. 59-201,046, No. 59-2
No. 01,047, No. 59-201,048, No. 59-
No. 201,049, No. 61-170,733, No. 61
-270,744, 62-948, 63-23
No. 4,244, No. 63-234,245, No. 63-2
Examples include the groups described in No. 34,246.

Examples of redox compounds having a hydrazine structure according to the present invention, in which the hydrazine moiety is oxidized and a subsequent reaction releases a photographically useful compound, include the following general formula (R-1), general formula (R-2), represented by the general formula (R-3).

[0021]

[C5]

In these formulas, R1, R2, G1,
The definitions of A1 and A2 are the same as in general formula (N-1), and A3 has the same meaning as A1 or -CH2CH(A4)-
(Time) represents t-PUG. A4 is a nitro group, cyano group, carboxyl group, sulfo group or -G1-
Represents G2-R1-. Time represents a divalent linking group, and t represents 0 or 1. PUG stands for a photographically useful group.

[0023] As will be explained in more detail, R1, G1
, A1 and A2, the explanation given for general formula (N-1) applies as is, and preferred examples, preferred substituents, etc. are also the same.

General formula (R-1), (R-2), (R-3
), the alkyl group represented by R2 is:
Preferably it is an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). R2 may be substituted, and as the substituent, a substituent can be applied to R1. A3 is a hydrogen atom, -CH2CH(A4
)-(Time)t-PUG is preferred.

General formula (R-1), (R-2), (R-3
), Time represents a divalent linking group and may have a timing adjustment function. The divalent linking group represented by Time represents a group that releases PUG from Time-PUG released from the oxidized product of the redox mother nucleus through one or more reaction steps.

[0026] As the divalent linking group represented by Time, for example, US Pat.
No. 4-145,135), which releases PUG through an intramolecular ring-closing reaction of p-nitrophenoxy derivatives; US Pat.
U.S. Pat. No. 4,330,617 and U.S. Pat. No. 4,446, which release PUG by an intramolecular ring-closing reaction after ring cleavage as described in U.S. Pat.
, No. 216, No. 4,483,919, JP-A-59-1
No. 21,328, etc., which releases PUG with the production of acid anhydride through an intramolecular ring-closing reaction of the carboxyl group of a succinic acid monoester or its analog; US Pat. No. 4,409,323; No. 4,421,845,
Research Disclosure Magazine No. 21,228
(December 1981), U.S. Patent No. 4,416,977
No. (JP-A No. 57-135,944), JP-A No. 58-2
No. 09,736, No. 58-209,738, etc., in which quinomonomethane or an analog thereof is generated by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group, and PUG is released. U.S. Patent No. 4,420,554
No.), JP-A-57-135,945, JP-A No. 57-188
, No. 035, No. 58-98,728 and No. 58-2
P from the γ-position of the enamine by electron transfer of the enamine structure-containing part of the nitrogen-containing heterocycle described in No. 09,737, etc.
Those that release UG; those that release PUG through an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle described in JP-A No. 57-56,837 ; U.S. Patent No. 4,146,
No. 396 (JP-A-52-90932), JP-A-59-
No. 93,442, JP-A-59-75475, JP-A-6
0-249148, JP-A-60-249149, etc., which release PUG with the production of aldehydes; JP-A-51-146,828, JP-A-57-179,
842 and 59-104,641 which releases PUG with decarboxylation of the carboxyl group; -O-
COOCR a R b-PUG (Ra and Rb represent monovalent groups), which releases PUG with decarboxylation and subsequent generation of aldehydes; JP-A-60-7,429 U.S. Pat. No. 4,438 which releases PUG with the formation of isocyanates as described in US Pat. No. 4,438.
Examples include those which release PUG through a coupling reaction with an oxidized form of a color developer, as described in, eg, No. 193 of ``Color Developer''.

Specific examples of these divalent linking groups represented by Time can be found in JP-A-61-236,549;
It is also described in detail in Japanese Patent Application No. 63-98,803.

PUG stands for (Time)t-PUG or a compound that is photographically useful as PUG. Photographically useful groups include, for example, development inhibitors, development accelerators, nucleating agents, couplers, diffusible or non-diffusible dyes, desilvering accelerators, desilvering inhibitors, silver halide solvents. Competitive compounds, developing agents, auxiliary developing agents, fixing accelerators, fixing inhibitors, image stabilizers, toning agents, processing dependency improvers, halftone dot improvers, color image stabilizers, photographic dyes, interfaces Examples include activators, hardeners, desensitizers, contrast agents, chelating agents, optical brighteners, acids, bases, and precursors thereof.

As a specific example of PUG, conventionally known ones are useful, for example, US Pat. No. 424,896
No. 2, No. 4409323, No. 4438193, No. 4
No. 421845, No. 4618571, No. 465251
No. 6, No. 4861701, No. 4782012, No. 4
No. 857440, No. 4847185, No. 447756
No. 3, No. 4438193, No. 4628024, No. 4
Those described in European Patent No. 618571, European Patent No. 4741994, European Patent Publication No. 193389A, European Patent Publication No. 348139A, or European Patent Publication No. 272573A are used.

The PUG is preferably a bleach accelerator (desilvering accelerator), a development inhibitor, a dye (including one that becomes a dye after cleavage), an electron transfer agent, or a coupler.

[0031] Preferred examples of the bleaching accelerator are as follows. -S-R11-COOH, -S-R11-OH, -S-
R12-COOH, -S-R11-NR13R14 In the above, R11 represents an alkylene group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. However, in the chain of the alkylene group -
O-, -CO-, -OCO-, -CONH-, -S-,
A divalent group of -SO2- or -SO2NH- may be present (for example, -S(CH2)2-S-CH2C
bleach accelerators such as OOH). R12 is a divalent heterocyclic group (a 5- to 6-membered ring having 1 to 5 carbon atoms and containing one or more oxygen atoms, sulfur atoms, or nitrogen atoms as heteroatoms; for example, a divalent pyridine ring, a divalent triazole ring, represents a group containing a divalent tetrazole ring) or a phenylene group. R13 and R14 represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.

When PUG represents a dye, P during development processing
When cleaved as UG, it becomes the desired hue, which is used as a pigment (or dye), with the general formula (R
The compound represented by -1), (R-2) or (R-3) itself has the desired hue and may flow out of the photographic layer by being cleaved as PUG during development.

Examples of dyes bonded to chromophores or auxochromes include the following. -X1 -R15-N=N-R16 In the formula, X1 represents an oxygen atom, a sulfur atom or an imino group, R15 represents an arylene group or an unsaturated heterocyclic group, and R16 represents an aryl group or a heterocyclic group. Here, when X1 represents an imino group, an alkyl-substituted imino group (1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, for example -
N(C2H5)-, -N(C12H25)-), aryl-substituted imino group (6 to 20 carbon atoms, preferably 6 to 20 carbon atoms)
10. For example, -N(C6H5)-) is a preferred example. When R15 represents an arylene group, it has 6 to 20 carbon atoms,
Preferred examples include 6 to 10 arylene groups, such as 1,2-phenylene and 1,4-phenylene. When R15 represents an unsaturated heterocyclic group, it is a 5- to 8-membered ring having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and containing at least one of oxygen, sulfur, or nitrogen atoms as a hetero atom, preferably 5 to 8 carbon atoms. It is a 6-membered ring. Examples include divalent pyrazole, imidazole, pyrrole or thiophene. The groups represented by R15 and R16 preferably have one or more substituents, and at least one of those substituents
A particularly preferred example is when these are the substituents listed for R1 above.

PUG represents a dye, general formula (R-1)
, (R-2) or (R-3) itself is used as a dye, and when PUG flows out (or decolorizes) from the photographic layer after cleavage during development processing, these dyes can be used, for example, as follows. It is something.

[0035]

[C6]

In the formula, R16 has the same meaning as explained above. R17, R18 and R19 represent a substituent or a hydrogen atom, but none of the three are hydrogen atoms. R20 has the same meaning as R16. X2 represents an oxygen atom, a sulfur atom or an imino group. *marks indicate general formula (R-1
), (R-2) or (R-3). The above also includes cases where a cyclic structure is formed. They are for example R17 and R18
, R16 and R19, and R20 and R16 are respectively connected to form a ring. A preferred example of the ring structure is a 5- or 6-membered ring. When R17, R18 and R19 are substituents, electron-withdrawing substituents are preferred examples. For example, acyl group, cyano group, alkoxycarbonyl group,
Preferred examples include those containing at least one sulfonyl group, carbamoyl group, nitro group, sulfamoyl group, or aryloxycarbonyl group. Detailed explanations of these are the same as those for R5 above. A preferred example of the group represented by R17 is one having at least one electron-donating group as a substituent. Examples of electron-donating groups include amino groups (0 to 30 carbon atoms, preferably 0 to 20 carbon atoms; for example, diethylamino, bis(methoxycarbonylmethyl)amino), alkoxy groups (1 to 20 carbon atoms);
30, preferably 1-20. Typical examples are methoxy, ethoxy) and hydroxyl groups.

When PUG is an electron transfer agent, 3-pyrazolidones are preferred examples. Particularly preferably, it is expressed by the following formula.

[0038]

[C7]

In the formula, R21 and R22 represent a substituent, a represents an integer of 0 to 4, and b represents an integer of 0 to 3. R21 is preferably an alkyl group (having 1 carbon number
~10, preferably 1-5. e.g. methyl, ethyl),
Alkoxy group (1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, e.g. methoxy, ethoxy, butoxy), halogen atom (
For example, chloro, bromo), alkylthio groups (1 to 1 carbon atoms)
10, preferably 1 to 5, e.g. methylthio, butylthio), acyloxy group (2 to 10 carbon atoms, preferably 2
~6. For example, acetoxy, benzoyloxy), amino group (0 to 12 carbon atoms, preferably 0 to 8 carbon atoms, such as diethylamino, dibutylamino), acylamino group (2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as acetamide, benzamide), Sulfonamide group (1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, e.g. methanesulfonamide, benzenesulfonamide), aryl group (6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, e.g. phenyl, naphthyl) or aryloxy group (6 to 10 carbon atoms, for example phenoxy). Typical examples of R22 include an alkyl group and an aryl group, and their explanations are the same as above. When a and b represent a plurality, a plurality of R21
and R22 each represent the same or different.

When PUG is a coupler, known couplers are useful. For example, phenol, naphthol (attached at the oxygen atom), pyrazolone (attached at the oxygen atom in the enol form), pyrorazolotriazole (attached at the nitrogen atom), or acylacetanilide (attached at the oxygen atom in the enol form) ).

When PUG is a development inhibitor, known development inhibitors are useful. Examples of common known development inhibitors include, for example, T.H.
s) Author: The Theory of the Photographic
The Theory of the Pho
4th edition, 1
977, published by Macmillan, 3
Pages 96 to 399 and Patent Application No. 56 of Patent Application No. 93487/1999
It is described on pages 69 to 69. These development inhibitors are preferably substituted, and examples of the substituent include those listed as the substituent for R1 in general formula (N-1), and these groups are preferably substituted. Good too.

Further, general formulas (R-1), (R-2), (R
-3), R1 or -(Time)t -P
UG contains ballast groups commonly used in immobile photographic additives such as couplers, general formulas (R-1), (
A group that promotes adsorption of the compound represented by R-2) or (R-3) to silver halide may be incorporated. The explanation given for general formula (N-1) applies as is to these ballast groups and adsorption promoting groups. Specific examples of the hydrazide compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0043]

[Chemical formula 8]

[0044]

[Chemical formula 9]

[0045]

[Chemical formula 10]

[0046]

[Chemical formula 11]

[0047]

[Chemical formula 12]

[0048]

[Chemical formula 13]

[0049]

[Chemical formula 14]

[0050]

[Chemical formula 15]

[0051]

[Chemical formula 16]

[0052]

[Chemical formula 17]

[0053]

[Chemical formula 18]

[0054]

[Chemical formula 19]

[0055]

[C20]

[0056]

[C21]

[0057]

[C22]

[0058]

[C23]

[0059]

[C24]

[0060]

[C25]

[0061]

[C26]

[0062]

[C27]

[0063]

[C28]

[0064]

[C29]

[0065]

[C30]

[0066] In addition to the above-mentioned hydrazide compounds used in the present invention, for example, RESEARCH
DISCLOSURE Item 23516 (198
November 3rd issue, P. 346) and the documents cited therein, U.S. Pat. Nos. 4,080,207 and 4,269,9.
No. 29, No. 4,276,364, No. 4,278,74
No. 8, No. 4,385,108, No. 4,459,347
No. 4,560,638, No. 4,478,928, British Patent No. 2,011,391B, JP-A-60-179
, No. 734, No. 62-270, 948, No. 63-29
, No. 751, No. 61-170, 733, No. 61-27
No. 0,744, No. 62-948, EP217,310
No., US 4,686,167, Japanese Patent Publication No. 62-178,
No. 246, No. 63-32, 538, No. 63-104,
No. 047, No. 63-121, 838, No. 63-129
, No. 337, No. 63-223, 744, No. 63-23
No. 4,244, No. 63-234,245, No. 63-2
No. 34,246, No. 63-294,552, No. 63-
No. 306,438, JP-A No. 1-100,530, same 1
-105,941, 1-105,943, JP-A No. 1-10,233, JP-A-1-90,439, JP-A-1-276,128, JP-A-1-280,747,
No. 1-283,548, No. 1-283,549, No. 1-285,940, No. 63-147,339, No. 6
No. 3-179,760, No. 63-229,163, Japanese Patent Application No. 1-18,377, No. 1-18,378, No. 1
-18,379, 1-15,755, 1-16
, No. 814, No. 1-40,792, No. 4-42, 61
No. 5, No. 1-42,616, No. 1-123,693, No. 1-126,284, JP-A-61-213,84
No. 7, No. 62-260,153, Patent Application No. 1-102,
No. 393, No. 1-102, 394, No. 1-102, 3
No. 95 and No. 1-114,455 can be used. Furthermore, a compound represented by general formula (N-1) and a compound represented by general formula (N-1) and general formula (
It can also be used in combination with a compound represented by R-1), (R-2) or (R-3).

The method for synthesizing the hydrazide compound used in the present invention is described, for example, in JP-A-61-213,847 and JP-A-62-847.
No. 260,153, U.S. Patent No. 4,684,604;
Patent Application No. 63-98,803, U.S. Patent No. 3,379,
No. 529, No. 3,620,746, No. 4,377,6
No. 34, No. 4,332,878, JP-A-49-129
, No. 536, No. 56-153, 336, No. 56-15
No. 3,342, etc.

The hydrazide compound of the present invention is used in an amount of 1.times.10@-6 to 5.times.10@-1, more preferably 1.times.10@-5 to 1.times.10@-1 mol per mole of silver halide.

The hydrazide compounds of the present invention can be used in suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellulose. It can be used by dissolving it in, etc. In addition, by the already well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and then mechanically emulsified and dispersed. You can also create and use things. Also,
Polytert-butylacrylamide, polymethyl methacrylate, polyvinyl acetate, etc. are dissolved together with the above-mentioned auxiliary solvent, and if necessary the above-mentioned oil, etc.,
An emulsified dispersion can also be created and used mechanically. Alternatively, a powder of a redox compound can be dispersed in water using a ball mill, a colloid mill, or an ultrasonic wave, using a method known as a solid dispersion method. When used as an emulsified dispersion, it may be preferable to remove the auxiliary solvent (by heating and vacuum distillation, ultrafiltration, washing with Nudel water, etc.) as necessary.

The water-insoluble oil-soluble compound of the present invention will be explained. Examples of water-insoluble oil-soluble compounds are represented by the following general formulas (A) and (B). General formula (A)

[0071]

[Chemical formula 31]

General formula (B)

[0073]

[C32]

In the formula, R1 to R5 and R21 to R2
5 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, a sulfo group, a carboxyl group, a carbamoyl group, a sulfamoyl group, Sulfonyl group, sulfinyl group, ester group, amino group which may have a substituent, acyl group and -X-R0
represents. Here, X represents -O- or -S-, and R
0 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an ester group. R
20 represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Among R1 to R5 and R21 to R25, the groups in ortho positions may be bonded to each other to form a 5- to 7-membered ring, and R20 and R21 or R20 and R25 may be bonded to each other to form a 5- to 7-membered ring. You may.

The compounds represented by formulas (A) and (B) will be explained in more detail. R1 to R5 and R
21 to R25 may be the same or different, and each represents a hydrogen atom, an alkyl group (a linear, branched or cyclic alkyl group such as methyl, ethyl, isopropyl, tert-butyl, benzyl, cyclohexyl, octyl, decyl,
hexadecyl, octadecyl), alkenyl groups (e.g. vinyl, allyl, oleyl, cyclohexenyl), alkynyl groups (e.g. ethynyl, 2-propynyl, 2-octenyl, 3-octadecenyl), aryl groups (e.g. phenyl, naphthyl), hetero Cyclic group (a 5- to 7-membered cyclic group having at least one oxygen atom, sulfur atom, or nitrogen atom as a ring constituent atom, such as furyl, pyrrolyl,
imidazolyl, pyrazolyl, pyridyl, pyrazyl, indolidyl, 3H-indolyl, xanthenyl, pteridyl, furazolyl, imidazolinyl, pyrazolidinyl, piperidyl, isothiazolyl), halogen atoms (e.g.
fluorine atom, chlorine atom, bromine atom), cyano group, nitro group, sulfo group, carboxyl group, carbamoyl group (e.g. dimethylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl), sulfamoyl group (e.g. butylsulfamoyl, phenylsulfamoyl, diethylsulfamoyl), sulfonyl groups (e.g. methanesulfonyl, benzenesulfonyl), sulfinyl groups (e.g. methanesulfinyl, benzenesulfinyl), ester groups (here we mean those whose free valence is on the carbonyl side, e.g. butoxycarbonyl) , hexadecyloxycarbonyl, phenyloxycarbonyl), amino groups that may have substituents (e.g. amino group, dialkylamino group, monoalkylamino group, anilino group, acylamino group, imido group, ureido group, urethane group, sulfone group) amide group), an acyl group (eg acetyl, benzoyl) and -X-R0. Here, X is -O- or -S-
, and R0 represents an alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, carbamoyl group, sulfamoyl group, or ester group in the same meaning as R1 to R5 and R21 to R25. R20 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group in the same meaning as R1 to R5 and R21 to R25. R1~5, R21~
25, the groups at mutually ortho positions may combine to form a 5- to 7-membered ring, and R20 and R21 or R20 and R
25 may be bonded to each other to form a 5- to 7-membered ring. R
Each group of 0 to 5 and R20 to 25 includes those further substituted with a substituent.

Among the compounds represented by the general formula (A), preferred compounds in terms of the number of carbon atoms are those in which the total number of carbon atoms in R1 to R5 is 6 or more, more preferably 8 or more, and most preferably 1.
It is 0 or more. On the other hand, among the compounds represented by the general formula (B), the total number of carbon atoms in R20 to R25 is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more. Further, among the compounds represented by the general formula (A), R1 to R5 preferably have a Hammett's σ value of 0 or more, more preferably 0.2 or more, and most preferably 0.4 or more. On the other hand, among the compounds represented by the general formula (B), preferred are -0.2 or more, more preferably 0 or more, and most preferably 0
．． It is 2 or more.

Among the compounds represented by general formula (A),
A preferred structure is represented by general formula (AI). General formula (A-I)

[0078]

[Chemical formula 33]

In the formula, R1 to R4 represent the groups defined in general formula (A). Y represents -CO-, -SO2-, R' is an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group. R' is Y is -CO-
Further represents an alkoxy group, an alkenoxy group, an alkynoxy group, an aryloxy group, or a heterocyclic oxy group. Further, when Y is --SO2 --, R' represents an amino group which may further have a substituent. Below is the general formula (A
) and (B) are shown below,
This does not limit the invention of the present application.

[0080]

[C34]

[0081]

[C35]

[0082]

[C36]

[0083]

[C37]

[0084]

[C38]

[0085]

[C39]

[0086]

[C40]

[0087]

[C41]

[0088]

[C42]

[0089]

[C43]

[0090]

[C44]

[0091]

[C45]

[0092]

[C46]

[0093]

[C47]

[0094]

[C48]

[0095]

[C49]

The compounds represented by the general formulas (A) and (B) are manufactured by S.I. R. Sandler, W. Karo, “O
rganic Functional Group P
"reparation", vol.1, Academ
ic ('68), p253, C. E. Rehberg
, Org. Synth. , III, 146 ('55),
YaM. Neeman et. al. , J. Org. C
hem. , 21,667 ('56).

The pKa of the compound of the present invention was measured as follows. The measurement was performed by dissolving 5 x 10-5 mol of the compound to be measured in a mixed solvent of 10 ml of distilled water and 40 ml of ethyl alcohol, and adding 0.2N-NaOH to the solution. Among specific compound examples, measurement examples are shown in Table 1.

[0098]

[Table 1]

The compounds of the invention can be used in suitable water-miscible organic solvents such as alcohols (methanol, ethanol,
propanol, fluorinated alcohols, etc.), ketones (
(acetone, methyl ethyl ketone, etc.), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. Preferably, dibutyl phthalate, tricresyl phosphate, N,N, diethyl laurylamide, etc. are dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and then mechanically dispersed by a well-known emulsification dispersion method. An emulsified dispersion can also be prepared and used. Also, poly tert
A powder of the compound of the present invention is added to water using a polymer such as butylacrylamide, polymethyl methacrylate, polyvinyl acetate, etc. and, if necessary, the above-mentioned oil, or a method well known as a solid dispersion method, using a ball mill or a colloid mill. Alternatively, it can also be used after being dispersed by ultrasonic waves. It can also be used by dissolving it with an auxiliary solvent and the like to create an emulsified dispersion. More preferably, the hydrazide compound of the present invention is dissolved together with the above-mentioned oil auxiliary solvent and, if necessary, the above-mentioned polymer, etc., and used as a co-emulsion with the hydrazide compound. When used as an emulsified dispersion, it may be preferable to remove the auxiliary solvent (by heating and vacuum distillation, ultrafiltration, washing with nude water, etc.) as necessary.

[0100] The amount of the compound of the present invention to be added is not particularly limited, but if necessary, the amount of the compound added to the hydrazide compound may be
1-300 mol%, preferably 2-200 mol%
It can be used by adding 1%, more preferably 5 to 150 mol%. There are no particular restrictions on the layer to which the compound of the present invention is added, but a layer containing the hydrazide compound,
And/or it can be used by being added to a layer adjacent thereto. Preferably, it is used in the same layer as the hydrazide compound.

The silver halide emulsion used in the silver halide emulsion layer of the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide, and the like. The emulsion is
Containing a rhodium salt is preferable in terms of obtaining ultra-high contrast images. It is desirable to select the optimum rhodium salt content depending on the grain size of the silver halide emulsion, the method and degree of chemical sensitization, etc., and testing methods for selection are well known to those skilled in the art. be. Usually, preferably from 1 x 10-8 mol to 1 x 1 mol of silver halide.
It is used in a range of 10-4 mol. Rhodium salts preferably used in the present invention include, for example, rhodium dichloride,
Examples include rhodium trichloride and rhodium ammonium hexachloride.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly preferably 0.5 μm 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.

The silver halide grains in the photographic emulsion are cubic,
It may have a regular crystal shape such as an octahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or it may have a composite shape of these crystal shapes. It may be. 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.

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. Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers that have a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and dyes that are safe against safelight light when handled as bright-room sensitive materials. Mainly from 350nm to 600nm to increase
A dye having substantial light absorption in the region is used. It varies depending on the molar absorption coefficient of the dye, but usually 10-2 g/m2
It is added in a range of ~1 g/m2. Preferably 50mg
~500mg/m2. Specific examples of dyes are given in JP-A-63
-64039, some of which are listed below.

[0105]

[C50]

[0106]

[C51]

The above-mentioned dye is dissolved in a suitable solvent [for example, water, alcohol (such as methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] to form the non-photosensitive hydrophilic dye of the present invention. Added to the coating solution for colloid layer. These dyes are 2
It is also possible to use a combination of two or more species. The dye of the present invention is
The necessary amount is used to allow handling in a bright room. The specific amount of dye used is generally 10-3g/m2 to 1g/m
2, in particular a preferred amount in the range 10-3 g/m2 to 0.5 g/m2.

Gelatin is advantageously used as a binder or protective colloid for photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol partial acetal, poly-N
- A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The silver halide emulsion used in the method of the present invention may not 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 gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. A specific example is US Patent 2,
No. 448,060, British Patent No. 618,061, etc. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention. Specific examples of spectral sensitizing dyes are given in Japanese Patent Application No. 2-123683, pages 49 to 8.
Examples include those described on page 5 and pages 77 to 124 of JP-A-62-215272.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
benzothiazoles, nitrobenzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1, 3,
3a, 7) tetrazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, etc.), aldehydes (glutaraldehyde, etc.), N
- Methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-
vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-
(triazine, etc.), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared according to the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration). Various surfactants may be included for various purposes such as increasing contrast, increasing contrast, and increasing sensitization. For example, saponin (
steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines, amides, polyethylene oxide adducts of silicone),
Nonionic surfactants such as alkyl esters such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonic acids salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters amphoteric surfactants such as alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or hetero Cationic surfactants such as ring-containing phosphonium or sulfonium salts can be used. Further, compounds described in JP-A No. 62-215272, pages 649 to 688, etc. can be used. Polymer latexes such as polyalkyl acrylates can be included for dimensional stability.

[0114] As a development accelerator or a nucleation infection development accelerator suitable for use in the present invention, Japanese Patent Application Laid-Open No. 53-77
616, 54-37732, 53-137, 133
, 60-140, 340, 60-14959, etc., and various other compounds containing N or S atoms are effective. Next, specific examples are listed.

[0115]

[C52]

[0116]

[C53]

[0117]

[C54]

[0118] The optimum amount of these accelerators to be added varies depending on the type of compound, but it is 1.0 x 10-3 to 0.5 g/m.
2, preferably in the range of 5.0 x 10-3 to 0.1 g/m2. These promoters are dissolved in a suitable solvent (H2O, alcohols such as methanol and ethanol, acetone, dimethylformamide, methylsolserve, 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 and high sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a pH 13 developer described in US Pat. No. 2,419,975.
It is not necessary to use a highly alkaline developer close to that of 100%, and a stable developer can be used. That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0.
Contains 15 mol/liter or more, pH 10.5-12.3
In particular, a sufficiently high contrast negative image can be obtained using a developer having a pH of 11.0 to 12.0. There are no particular limitations on the developing agent that can be used in the method of the present invention, such as dihydroxybenzenes (e.g. hydroquinone),
-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-
(aminophenol) etc. can be used alone or in combination. The silver halide light-sensitive material of the present invention is particularly suitable for processing with a developer containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, in this developer, dihydroxybenzenes are used in an amount of 0.05 to 0.5 mol/liter, and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol/liter or less. Also, US Patent No. 4,269,929
As described in the above issue, it is also possible to increase the development speed and shorten the development time by adding amines to the developer. As the developer used in the present invention,
Amino compounds described in Japanese Patent Application No. 1-294185 can be used. The developer solution also contains pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). ), a development inhibitor or an antifoggant may be included. 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 thiosulfates and thiocyanates, 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.

[0120] The processing temperature in the method of the present invention is usually 18
Selected between ℃ and 50℃. Although it is preferable to use an automatic processor for photographic processing, according to the method of the present invention, the total processing time from the time the photosensitive material is put into the automatic processor until it comes out can be set to 60 seconds to 120 seconds. , sufficiently ultra-high contrast negative gradation photographic characteristics can be obtained. In the developer of the present invention, compounds described in JP-A No. 56-24,347 can be used as silver stain preventive agents. A compound described in JP-A-61-267759 can be used as a solubilizing agent added to the developer. Furthermore, the pH used in the developer
As a buffering agent, a compound described in JP-A-60-93,433 or a compound described in JP-A-62-186259 can be used. Examples are shown below to explain embodiments of the present invention.

[0121]

[Example] Example 1 <How to make a silver halide emulsion> Emulsion-A 0.37 mol of silver nitrate aqueous solution and (NH4)3Rh equivalent to 1.0 x 10-7 mol per mol of silver in the finished emulsion.
Cl6 and 2x10-7 mol of K3IrCl6, 0.
A halogen salt aqueous solution containing 11 moles of potassium bromide and 0.27 moles of sodium chloride was mixed with sodium chloride and 1,
It was added to an aqueous gelatin solution containing 3-dimethyl-2-imidazolidinethione by a double jet method at 45°C for 12 minutes while stirring, and the average particle size was 0.20 μm.
Nucleation was performed by obtaining silver chlorobromide grains having a silver chloride content of 70 mol %. Subsequently, in the same manner, 0.63 mol of silver nitrate aqueous solution, 0.19 mol of potassium bromide, and 0.4 mol of silver nitrate aqueous solution were added.
A halogen salt aqueous solution containing 7 mol of sodium chloride was added over 20 minutes by a double jet method. After that, conversion was carried out by adding 1 x 10-3 mol of KI solution per mol of silver, washing with water by the flocculation method according to the conventional method, adding 40 g of gelatin, and adjusting the pH to 6.5.
The pAg was adjusted to 7.5, and 7 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate, and 8 mg of chloroauric acid were added per mole of silver, heated at 60°C for 45 minutes, and chemically sensitized. ,3,
150 mg of 3a,7-tetrazaindene and Proxel as preservative were added. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%) Emulsion-B Emulsion-A (NH4)3RhCl6 Completed emulsion Silver 1
The emulsion was changed to 1.8 x 10-7 mol per mol
Prepared in exactly the same manner as A.

<Preparation of emulsified dispersion of hydrazide compound> Each liquid was prepared according to the emulsion recipe having the composition shown in Table 2, and after melting at 60°C, liquid I and liquid II were mixed, and a high-speed stirrer (homogenizer, Nippon Seiki After creating a microparticle emulsion (manufactured by Seisakusho), water was added to make up to 100 g. The average particle size was 0.13-0.16μ.

[0123]

[Table 2]

(Preparation of coating sample) UL, EMU, ML, Sample No. 1 was coated so as to have a layer structure of EMO and PC. 101-10
8 was created. The preparation method and coating amount of each layer are shown below. (UL) Gelatin 10g, 20wt% based on gelatin
Polyethyl acrylate, compound (a), was added to gelatin in an amount of 2 wt%, water was added to give a final volume of 250 ml, and the gelatin was coated at 0.5 g/m2. (EMU) After dissolving emulsion-A together with gelatin at 40°C, the following compound S-1 was added as a sensitizing dye at 3.6×
10-4 mol/mol Ag, 5-methylbenztriazole 6.5 mg/m2, 4-hydroxy-1,3,3a,
7-tetrazaindene 1.3 mg/m2, 1-phenyl, 5-mercaptotetrazole 1 mg/m2, the following compound (a) 50 mg/m2, 15 wt% based on gelatin
of polyethyl acrylate, 15wt to gelatin
% of the following compound (e), 4wt% of the following compound (b) relative to gelatin as a gelatin hardening agent, and a nucleating agent (
c) 1.6 x 10-3 mol/molAg Nucleating agent (d) 5.4 x 10-6 mol/molAg were added and coated to give Ag 3.6 g/m2.

[0125]

[C55]

[0126]

[C56]

(ML) 10 g of gelatin, 20 wt% polyethyl acrylate based on gelatin, the above compound (
Add 2wt% of b) to gelatin, and the finished amount is 25%.
Add water to make 0 ml and add gelatin to 1.0 ml.
It was coated so that the amount was g/m2. (EMO) After dissolving the emulsion-B together with gelatin,
Compound S-1 was used as a sensitizing dye at 3.6 x 10-4 mol/
Mole Ag, 4-hydroxy-1,3,3a,7-tetrazaindene 1.0 mg/m2, hydrazide compound emulsified dispersion of the present invention (7.0 x 10- as hydrazide compound)
5 mol/m2), compound (a) 20
mg/m2, 20 wt% polyethyl acrylate based on gelatin, and 4 wt% compound (b) based on gelatin as a gelatin hardening agent, Ag0.4
g/m2 and gelatin 0.4 g/m2. (PC) Polymethyl methacrylate dispersion (average particle size 5 μ) in gelatin solution, and the following surfactant (F,
g) was added and coated so that gelatin was 0.5 g/m2 and polymethyl methacrylate was 0.5 g/m2.

[0128]

[C57]

The back layer was coated using the following recipe. [Back layer formulation] Gelatin

4g/m2 Matting agent
Polymethyl methacrylate (particle size 3.0-4.0μ
)

10mg/m2 latex polyethyl acrylate
2g/m2
Surfactant Sodium p-dodecylbenzenesulfonate 40mg/m2 Fluorine surfactant (III)
5mg/m2
Gelatin hardening agent; compound (b)
110m
g/m2 Dye Mixture of dyes [a], [b], [c] and [d] Dye [a]

53mg/m2
Dye [b]

14mg/m2 dye [c]

25mg/m2
Dye [d]

18mg/m2

[0130]

[C58]

[0131]

[C59]

Table 3 shows the developer formulation used in this example.

[0133]

[Table 3]

The photographic properties of FG-6 were determined using the developer with the above formulation.
These are the results of 30'' development at 34°C using a 60F automatic processor (manufactured by Fuji Photo Film Co., Ltd.), followed by fixing, washing, drying, and processing.The fixer was GR- manufactured by Fuji Photo Film Co., Ltd. F1 was used. [Image quality] 1. Evaluation of image quality (1) Creation of manuscript Monochrome scanner SCA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and special photosensitive material SF-100, a transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed in stages were created. At this time, the number of screen lines was 150 lines/inch. (2) Photography plate-making camera C manufactured by Dainippon Screen Co., Ltd.
After setting the above-mentioned original and the optical wedge at -440mm so that the stretching magnification was the same, the evaluation sample was exposed to light by irradiating it with a Xe lamp. At this time, exposure was performed so that 90% of the step wedge of the original was exposed to 10%. (3) Adjust the exposure amount as shown in evaluation (2) and adjust the exposure to the small dot side (
A five-grade evaluation (from 5 to 1) was performed in descending order of the gradation reproducibility (difficulty of halftone dot collapse) in simple shadow areas, which was the sum of the halftone dot percentages in the highlight areas (highlight areas). For intermediate performances of 3 to 5, a further ranking evaluation of 0.5 units was performed. 2. Evaluation of the image quality of line drawings After photographing a manuscript consisting of grade 7 Mincho and Gogic phototypesetting characters with a reflection density in the range of 0.5 to 1.2 using a Dainippon Screen camera (C-690), Development processing (34°C 30'') under the same conditions as photographic properties.
). The evaluation is done on a five-point scale.
5" represents the best quality and "1" represents the worst quality. The results are shown in Table 4.

[0135]

[Table 4]

As is clear from the results in Table 4, sample No. 1 containing no hydrazide compound in the EMO layer. Sample No. 101 was added with a hydrazide compound. In 101,
Both eye stretching and line drawing quality have improved, but it is still not enough. In contrast to these, sample No. 1 was prepared by co-emulsifying the compound of the present invention. 102 to 107, it can be seen that the image quality is significantly improved.

Example 2 The EMO emulsion of Example-1 was changed as shown in Table-5, and the amount of hydrazide compound was 1.
．． Sample No. 201
~213 was created. Performance evaluation was performed in the same manner as in Example-1. The emulsion formulation is shown in Table 5, and the results are shown in Table 6.

[0138]

[Table 5]

[0139]

[Table 6]

From the results in Table 6, sample No. Although the image quality is improved in 202, 208, 210, and 212 compared to 201, it is still insufficient. Sample No. of the present invention. 203
207, 209, 211, and 213, it can be seen that the image quality is clearly improved compared to the comparative sample containing only the hydrazide compound.

Example 3 <Preparation of an emulsified dispersion of a dye-releasing redox compound> Each liquid was prepared using an emulsified formulation having the composition shown in Table 7, and after melting at 60°C, liquids I and II were mixed,
Create a microparticle emulsion using a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Seisakusho), add water, and mix up-to-10.
It was set to 0g.

[0142]

[Table 7]

Preparation of Photosensitive Sheet Each layer was coated on a polyethylene terephthalate transparent support as follows to obtain a photosensitive sheet 301. (1) A mordant layer containing 3.0 g/m2 of gelatin and 3.0 g/m2 of the following polymer latex mordant.

[0144]

[C60]

(2) White reflective layer containing 18 g/m2 of titanium dioxide and 2.0 g/m2 of gelatin. (3) Carbon black 2.0g/m2 and gelatin 1
．． A light shielding layer containing 0 g/m2. (4) The following cyan dye-releasing redox compound 0.4
4g/m2, tricyclohexyl phosphate 0.09
g/m2, 2,5-di-t-pentadecylhydroquinone 0.008g/m2, and gelatin 0.8g/m2
A layer containing.

[0146]

[C61]

(5) Red-sensitive internal latent type direct positive silver bromide emulsion (silver amount 0.60 g/m2), gelatin 1.2 g/m2
m2, a red-sensitive emulsion layer containing 0.015 mg/m2 of the following nucleating agent and 0.13 g/m2 of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

[0148]

[C62]

(6) Layer containing 0.43 g/m2 of 2,5-di-t-pentadecylhydroquinone, 0.1 g/m2 of trihexyl phosphate and 0.4 g/m2 of gelatin. (7) The following magenta dye-releasing redox compound (0.50 g/m2), tricyclohexyl phosphate (0.12 g/m2), 2,5-di-t-
Pentadecylhydroquinone (0.009g/m2
) and gelatin (0.9 g/m2).

[0150]

[C63]

(8) Green-sensitive latent type direct positive silver bromide emulsion (silver content 0.45 g/m2, gelatin (0.75 g/m2)
m2), the same nucleating agent as layer (5) (0.013 mg/m
2) a green-sensitive emulsion layer containing: (9) Same layer as (6). (10) Yellow dye-releasing redox compound with the following structure (0.53 g/m2), tricyclohexyl phosphate (0.13 g/m2), 2,5-di-t-pentadecylhydroquinone (0.014 g/m2), and gelatin (0.7 g/m2).

[0152]

[C64]

(11) Blue-sensitive latent direct positive silver bromide emulsion (silver content: 0.60 g/m2), gelatin (1 g/m2)
), same nucleating agent as layer (5) (0.019 mg/m2)
A blue-sensitive emulsion layer containing. (12) Layer containing 1.0 g/m2 of gelatin. Next, coating was performed on a polyethylene terephthalate support in the following order to prepare a cover sheet.

(1) A neutralization layer containing 22 g/m 2 of acrylic acid-butyl acrylate (mole ratio 8:2) copolymer having an average molecular weight of 50,000. (2) Cellulose acetate with an acetylation degree of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of sample) and styrene-maleic anhydride with an average molecular weight of about 10,000 (molar ratio Neutralized timing layer containing 4.5 g/m2 of 1:1) copolymer in a weight ratio of 95:5.

(3) Styrene/butyl acrylate/
Acrylic acid/N-methylolacrylamide weight ratio: 4
Polymer latex emulsion polymerized in a ratio of 9.7/42.3/4/4 and methyl methacrylate/acrylic acid/N
- A polymer latex prepared by emulsion polymerization of methylol acrylamide at a weight ratio of 93:3:4 with a solid content ratio of 6:4.
A layer containing a total solids content of 1.6 g/m2.

Next, the fourth layer, seventh layer, and
Photosensitive sheets 302 to 303 were prepared in exactly the same manner as photosensitive sheet 301 except that the dye-releasing redox compound in the 10th layer was replaced with the emulsion shown in Table 7.

Exposure and development of photosensitive sheets A light source of 2854°K was used for the photosensitive sheets 301 to 303,
and a color filter (manufactured by Fuji Photo Film Co., Ltd., B)
PB-45 (B), BPB-55 (G), SC-62 (
After exposure was carried out through an optical wedge color-separated using R)), the cover sheets were overlapped, and between the two sheets, 85% of the processing solution shown in Table 8 was applied at 25°C.
It was expanded to a thickness of μ. (Development was carried out with the help of a pressure roller.) After 2 minutes, 5 minutes, and 1 hour after developing these samples, the Dmax and Dmin areas of the transferred images were measured using a color reflection densitometer (Fuji Photo Film). The concentration was measured using FSD (manufactured by Co., Ltd.). The results are shown in Table 9.

[0158]

[Table 8]

[0159]

[Table 9]

From the results in Table 9, photosensitive sheet 302 using only a hydrazide compound has a slightly faster dye image formation speed than photosensitive sheet 301, and the post-transfer (density in 1 hour versus 5 minutes) difference) becomes smaller, Dmin
However, the dye image forming speed, Dmax, is still insufficient. Photosensitive sheet 30 of the present invention
It can be seen that in Sample No. 3, Dmin was low, the dye image forming speed was very fast, and sufficiently high Dmax was obtained for all of B, G, and R.

Example 4 <Preparation of hydrazide compound emulsion> Each liquid was prepared according to the emulsion recipe having the composition shown in Table 10, and heated at 60°C.
After dissolving in liquid I and liquid II, a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Co., Ltd.) was used to create a fine particle emulsion.The auxiliary solvent was removed by vacuum distillation, and water was added. , up-to 100g.

[0162]

[Table 10]

<Preparation of coating sample> On a polyethylene terephthalate film (150μ) support having an undercoat layer (0.5μ) made of vinylidene chloride copolymer, layer configurations of EM and PC were sequentially applied from the support side. Sample No. 401-412 were created. The preparation method and coating amount of each layer are shown below. (EM) From the composition of (EMU) in Example-1, the nucleating agent (
Example-1 except that c) and nucleating agent (d) were removed.
EMU) was prepared in exactly the same manner as Ag3.6g/m2.
It was applied so that (PC) It was prepared and applied using exactly the same formulation as (PC) in Example-1. The sample prepared in this way is designated as sample No.
．． 413. Sample No. Sample No. 413 except that the emulsion shown in Table 10 was added to the (EM) layer. 41
Sample No. 3 was prepared in exactly the same manner as in Sample No. 3. 401-412 were created. The amount of emulsion added is 2.7 as a hydrazide compound.
The amount was set to x10-5 mol/m2. Also emulsion N
o. 401 to 403 are emulsion Nos. 404-40
The same weight as 6 was added.

[0164] These samples were exposed to light through an optical wedge using a 3200°K light source, and then developed in the same manner as in Example-1 using the developer used in Example-1. . The transmitted density of the developed sample was measured. Photographic characteristics were evaluated using Dmin, Dmax, γ (gamma), and relative sensitivity. The results are shown in Treatment Table 11.

[0165]

[Table 11]

From the results in Table 11, it can be seen that the compound (A) of the present invention
and sample No. using only compound (B). 402 and 403 are comparative sample Nos. 402 and 403 with no emulsion added. Exactly the same as 413, but with increased sensitivity. γup has no effect at all. or,
Sample No. using only a hydrazide compound. 404,
407 and 410 have significantly increased sensitivity,
Dmax hasn't reached its full potential yet. It can be seen that in all the samples of the present invention, the sensitivity is higher than when the hydrazide compound is used alone, the gradation becomes extremely hard, and a high Dmax can be obtained.

Example 5 Sample No. 4 of Example 4. 404~
Samples 501 to 507 were prepared in exactly the same manner as in Example 4, except that the amount of emulsion added in 406 was changed as shown in Table 12, and the exposure and development treatments were performed in exactly the same manner as in Example 4. . The results are shown in Table 12.

[0168]

[Table 12]

From the results in Table 12, sample No. of the present invention.
In samples No. 502 to 507, the amount of hydrazide compound applied was that of sample No. With the same amount as 501, high contrast, high sensitivity, and high Dma
x was obtained, and sample no. From the results of 504 and 507, sample No. Even with half the amount of hydrazide compound in Sample No. 501, sample No. Dmax, γ, equal to or higher than 501
Sensitivity can be obtained.

[0170]

Effects of the Invention The present invention provides a hydrazide compound that is oxidized by an oxidation product of a developer and then converted into a photographically useful compound or releases a photographically useful reagent by attack by a nucleophile, and a hydrazide compound that has a pKa value. Silver halide photosensitive materials containing water-insoluble and oil-soluble compounds with dissociative groups of 7.5 or more have excellent image quality such as sharpness, graininess, resolution, and halftone dot quality, and have photographic performance with a wide exposure latitude. was gotten.

Claims (4)

[Claims] Claim 1: In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion layer or other hydrophilic colloid layer is oxidized by an oxidation product of a developer. A hydrazide compound that transforms into a photographically useful compound or releases a photographically useful reagent upon attack by a nucleophile, and has a pKa value of 7.
1. A silver halide photographic material comprising a water-insoluble and oil-soluble compound having 5 or more dissociative groups and being less than neutral. Claim 2: The hydrazide compound has the general formula (N-1)
, general formula (R-1), general formula (R-2) and general formula (R
2. The silver halide photographic material according to claim 1, wherein the silver halide photographic material is selected from the compounds represented by -3). [Formula 1] In the formula, R1 represents an aliphatic group or an aromatic group, and R2
represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G1 represents a -CO- group, -SO2 - group, -SO-
group, -P(O)(G2-R2)- group, -COCO-
group, thiocarbonyl group or iminomethylene group,
G2 is a simple bond, -O- group, -S- group, or -
Represents an NR2- group. Both A1 and A2 represent a hydrogen atom, one of which is a hydrogen atom, and the other of which is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. A3 is synonymous with A1, (time) is 2
The valence group t represents 0 or 1. PUG stands for a photographically useful group. Claim 3: The water-insoluble oil-soluble compound has the general formula (A)
The silver halide photographic material according to claim 1, which is a compound represented by general formula (B). General formula (A) [Chemical formula 2] General formula (B) [Chemical formula 3] Claim 4: General formula (N-1), general formula (R-1)
, at least one compound of general formula (R-2) and general formula (R-3) and general formula (A) and/or general formula (
4. The silver halide photographic material according to claim 2, wherein the compound B) is co-emulsified.