JPH02287346A - Silver halide photographic sensitive material and image forming method using the material - Google Patents

Abstract

PURPOSE:To provide a high sensitivity and high contrast and to lessen the generation of pepper by providing one layer of silver halide emulsion layer on a base and incorporating specific compds. into the emulsion layer or other hydrophilic colloidal layer. CONSTITUTION:This photosensitive material has at least one layer of the silver halide emulsion layer on the base. At least of the compds. expresed by formula I, formula II and at least one of the compds. expressed by formula III are incorporated into the emulsion layer or other hydrophilic colloidal layers. In the formulas I, II, R<1> to R<4> respectively independently denote a hydrogen atom, substd. or unsubsted. alkyl group or aryl group; the case in which R<3> and R<4> are simultaneously the hydrogen atom is precluded. In the formula III, Z denotes N or CR<7>; R<5> denotes an alkyl group or aryl group substd. in >=1 with a sulfo nate group or carboxyl group; R<6> denotes a substd. or unsubstd. aryl group; R<8> denotes a hydrogen atom, substd. or unsubstd. alkyl group. The high sensitiv ity and high contrast are obtd. in this way and the generation of the pepper is lessened.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material that is extremely useful in photolithography processes for printing, and a method for forming ultra-high contrast negative images using the same.

[Prior art]

Since the photolithography process requires the formation of sharp halftone dot images or line drawings, an image forming system that exhibits extremely high contrast photographic characteristics (in particular, a gamma of 10 or more) is required.

Conventionally, for this purpose, a silver chloride content of at least 50
A lithium-type silver halide photographic light-sensitive material consisting of a silver chlorobromide emulsion of mol% or more is used, contains only hydroquinone as a developing agent, and has an extremely low sulfite ion concentration of 't1# (usually 0.1 mol/l or less). ) A method of processing with a Lith developer is known.

However, the Lith developer has a serious drawback in that it is subject to air oxidation due to the low concentration of sulfite ions in the solution, resulting in significant performance deterioration within a few days. In addition, it was difficult to achieve high sensitivity because a silver chlorobromide emulsion with a high silver chloride content had to be used.

On the other hand, as a technique for forming a high-contrast image using a stable developer, US Pat. .269.924, 4.311,781,
An image forming system using a specific hydrazine derivative disclosed in Japanese Patent No. 4,650.746 and the like has been proposed. According to this method, a surface latent image type silver halide photographic light-sensitive material to which a specific hydrazine derivative (generally an acylphenylhydrazine derivative) is added as a nucleating agent is mixed with 0.1
pH 11-12 containing 5 mol/1 or more sulfite.
A high-contrast image with a gamma of over 10 was obtained by processing with a stable developer of No. 3. Since it is permissible to add a high concentration of sulfite to this developer, the storage stability of the developer is dramatically improved compared to the lithium developer.

However, ultrahigh contrast imaging systems using the above-mentioned acylhydrazine derivatives have been found to have several drawbacks. In other words, by using the above image forming system, you can obtain a high-contrast image, and at the same time, you can obtain a clear image with a sharp black background.
This has become a major problem in the photolithography process.

4.1 Peraper is black black that occurs in unexposed areas, such as areas between halftone dots that should be undeveloped.
! Spots like 2 cause failures that significantly reduce the commercial value of the photolithography process.

There was a demand for an image forming system that could achieve high sensitivity and high contrast without causing blurring, and a system was proposed in Japanese Patent Application No. 63-23383.

However, this new imaging system has the disadvantage that the recovery density increases due to variations in sensitivity or gamma due to changes in the composition of the developer due to processing of large amounts of film or air oxidation. .

[Problem that the invention seeks to solve]

Accordingly, the first object of the present invention is to provide a silver halide photographic material and a method for forming a photographic image, which use a stable developer and exhibit extremely high sensitivity and high contrast, with a gamma of over 10.

The second object of the present invention is to process a large amount of film,
To provide a silver halide photographic light-sensitive material and a method for forming a photographic image, in which recovery density with a change in sensitivity or gamma does not increase even if the composition of a developer changes due to air oxidation.

A third object of the present invention is to provide a silver halide photographic light-sensitive material and a method for forming a photographic image in which the generation of particles is reduced.

[Means to solve the problem]

The above object of the present invention is to have at least one silver halide emulsion layer on a support, and to contain a compound represented by the following general formula (1) or (II) in the emulsion layer or other hydrophilic colloid layer. A negative silver halide photosensitive material characterized by containing at least one compound represented by the formula (III) and at least one compound represented by the general formula (III), and after imagewise exposure to this photosensitive material, 0.15 mol This was achieved by a method for forming an ultra-high contrast negative image, which is characterized in that it is developed with a developer containing sulfite ions of /1 or more and having a pH of 11 to 12.5.

General formula (1) General formula (■) [In the formula, R', R", R3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. However, R1 and R4 are the same ] General formula (III) [In the formula, Z is N or CR) (R? represents a hydrogen atom, a substituted or unsubstituted argyl group or an aryl group), R
"represents an alkyl group or aryl group substituted with one or more sulfonate groups or carboxyl groups. R6 represents a substituted or unsubstituted aryl group. R8 represents a hydrogen atom or a substituted or unsubstituted alkyl group.] The compound of general formula (III) of the present invention suppresses fog density and significantly improves permeability without inhibiting the sensitization and ultra-high contrast effects of the compound of general formula (I) or general formula (I[). Show effectiveness.

-8 The compound of formula (1) is the compound of general formula (1) or - general formula (I
It is preferably added to the same layer as the compound t), but it may be added to separate layers.

Next, the hydrazine derivative used in the present invention will be explained.

The hydrazine derivative used in the present invention has the following formula (1):
or a compound represented by (If).

General formula (1) General formula (II) In the above general formula (1) or (II), R1, R2, R3 and R4 are each independently a hydrogen atom, a straight chain, branched or cyclic group having 1 to 20 carbon atoms. It represents an unsubstituted or substituted alkyl group, a monocyclic or bicyclic unsubstituted or substituted aryl group.

Examples of the unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, hexyl group, cyclohexyl group, and cyclopentyl group.

Examples of substituents in the above-mentioned substituted alkyl group include:
A monocyclic or bicyclic unsubstituted or substituted aryl group (substituents include, for example, an alkyl group, a halogen atom,
hydroxyl group, alkoxyl group, alkylthio group, substituted amino group, ureido group, etc.), heterocyclic group (indole ring, imidazole ring, triazole ring, benzotriazole ring, tetrazole ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole) (rings, etc.), halogen atoms, hydroxyl groups, alkoxyl groups, etc.

Examples of substituted alkyl groups include benzyl group, phenethyl group, 2-chloroethyl group, 2-methoxyethyl group,
2-hydroxyethyl group, p-methylbenzyl group, P-
Isopropylbenzyl L p-hydroxybenzyl group,
p-methoxybenzyl group, p-methylthiobenzyl group,
Examples include p-aminobenzyl group, p-N,N-dimethylbenzyl group, p-NN-dimethylureidobenzyl group, and the like.

Examples of the unsubstituted aryl group include phenyl group,
Examples include naphthyl group.

Examples of the substituents of the substituted aryl group include an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, an alkoxyl group or alkylthio group having 1 to 10 carbon atoms, an amino group, a substituted amine group, and a ureido group. etc.

Substituted aryl groups include, for example, p-)lyl group, m-
Truly group, 0-tolyl group, p-isopropylphenyl L
p-chlorophenyl L O-chlorophenyl group, p-
Methoxyphenyl group, p-methylthiophenyl group, p-
Aminophenyl group, p-N, N-dimethylaminophenyl group, P-acetylaminophenyl group, p-hydroxyphenyl group, 0-hydroxyphenyl group, p-N, N-
Examples include dimethylureidophenyl group.

The substitution position of the formylhydrazino group in general formula (1) or (II) may be any of the 2- to 6-positions of the pyridine ring, but the 2-position is particularly preferred.

-IC Representative specific examples of the compound represented by formula (1) or (II) are shown below.

-t ■-10 ■ (t-static; tertiary amyl)! E) ■-16 ■ ■ ■ -13 ■ ■ -22 ~ ~ ■ ■ =25 ■ ■ (tBu: tertiary butyl group) ■ ■ ■ -28 0■ llz ■ O 1lC1h ■-31 ■ ■ -37 ■ -38 ■ llt ~ ■ ■ -43 ■ -48 ■ ■ ■ ■-45 ■-46 ■-47 ■ EightIt-5 ■-6 ■ ■-8 ■-14 ■-16 l-10 ■-11 ■ -12 ■-18 ■-19 ■-2O ■-21 ■-22 ■-23 ■-24 ■-29 ■-30 ■-31 ■-32 ■-26 ■-27 ■-28 ■-33 ■-34 ■-35 In order to incorporate the compound represented by the general formula (1) or (It) into a photographic light-sensitive material, the compound may be added to a surface latent image type photographic emulsion, or other hydrophilic colloids may be added. an emulsion layer or a non-light-sensitive layer consisting of a layer;
For example, it may be added to layers such as a protective layer, an intermediate layer, an anti-halogen layer, and a filter layer.

Preferably, it is added to a surface latent image type photographic emulsion.

When adding the compound of general formula (1) or (II) to a photographic emulsion, it can be added at any time from the start of chemical ripening to before coating, but it is best to add it after chemical ripening is completed. Most preferred.

In order to add the compound of general formula (1) or (If) to a photographic light-sensitive material, a method commonly used for adding additives to photographic emulsions can be used.

For example, water-soluble compounds should be prepared as aqueous solutions with appropriate concentrations, and compounds that are insoluble or sparingly soluble in water should be prepared in suitable organic solvents that are miscible with water, such as alcohols, ketones, esters, etc.
It may be dissolved in an amide or the like and added as a solution to the negative tone silver halide photographic emulsion or non-photosensitive hydrophilic colloid solution used in the present invention.

The amount of the compound represented by formula (1) or (U) added to the photographic light-sensitive material depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the type of fog inhibitor, etc. It is desirable to select the optimal amount. Usually, it is used in a range of io-' mol to 10-1 mol, preferably 10-3 mol to 5.times.10-'' mol, per mol of silver halide.

Next, the compound of general formula (1) used in the present invention will be explained.

General formula (I[[) (wherein Z is N or CR' (R7 represents a hydrogen atom, a substituted or unsubstituted alkyl group or aryl group),
R5 represents an alkyl group (preferably one having up to 20 carbon atoms) or an aryl group (preferably a phenyl group) substituted with one or more sulfonate or carboxyl groups, and these alkyl or aryl groups are further substituted with It may be substituted with other substituents such as a halogen atom, an alkoxy group, an aryloxy group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a cyano group, a hydroxyl group, an alkyl group, an alkoxycarbonyl group.

R1' represents a substituted or unsubstituted aryl group (preferably a phenyl group), and these aryl groups further include a halogen atom, an alkoxy group, an aryloxy group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, and a cyano group. , a hydroxyl group, an alkyl group, an alkoxycarbonyl group, etc., and electron-withdrawing substituents are particularly preferred. R8 represents a hydrogen atom or a substituted or unsubstituted alkyl group (preferably having up to 20 carbon atoms).

Specific examples of the compound represented by the general formula (III) used in the present invention are shown below, but the scope of the present invention is not limited to these compound examples.

SO, Na 5O, Na GOON COOH The compound represented by the general formula (Tll) of the present invention can be added in the same manner as the compound of the general formula (1) or (II), and is added in an amount of 1 mol of silver halide. 5xto-' per hit
It is preferable to contain mol to IXIO-2 mol, particularly preferably 1Xl0-5 mol to 5.times.10-3 mol.

In the present invention, the silver halide grains contained in the silver halide photographic emulsion layer include surface latent image type silver chloride, silver bromide, silver chlorobromide,
Either silver iodobromide or silver iodochlorobromide may be used. In the case of silver iodobromide or silver iodochlorobromide, the silver iodide content preferably does not exceed 10 mol %, particularly preferably up to 5 mol %. If silver chloride is included, it preferably does not exceed 70 mol% of the total silver halide, particularly preferably 50 mol%.

The silver halide grains used in the present invention have an average grain size of 0.
．． It is preferable to use a monodispersed emulsion in which the grain size is in the range of 1 to 0.7 μm and the grain size accounting for 90% of all grains is within ±40% of the average grain size.

Silver halide grains used in the present invention can be prepared using any known method. i.e. acid method,
Any of the neutral method, ammonia method, etc. may be used, and the reaction method of the soluble root salt and the soluble halogen salt may be a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof. One of the simultaneous mixing methods is to keep the silver ion concentration (pAg) constant in the liquid phase in which silver halide is produced, that is, the pAg chondral double jet method (C, D, J method). Monodisperse silver halide grains with uniform crystal shape and nearly uniform grain size can be obtained. In order to increase the contrast of the silver halide emulsion during the process of silver halide grain formation or physical ripening, a cadmium salt, iridium salt or rhodium salt may be present.

The binder contained in the silver halide photographic emulsion layer used in the present invention preferably does not exceed 250 g per mole of halide. Gelatin is most preferred as the binder, but hydrophilic colloids other than gelatin can also be used. For example, hydrophilic polymers such as albumin, casein, graft polymers of gelatin and other polymers, polyvinyl alcohol, and polyacrylamide can be used.

Although the silver halide emulsion used in the present invention does not need to be chemically sensitized, it is usually chemically sensitized.

As the chemical sensitization method, sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used, and particularly preferred chemical sensitization for carrying out the present invention is the sulfur sensitization method or the combination of sulfur sensitization and noble metal sensitization. This method combines one method, gold sensitization.

As the sulfur sensitizer, active gelatin, thiosulfur salts, thioureas, allylthiocarbamide, etc. can be used. HAuCfa as a gold sensitizer.

Au (SCN) z” salt, Au (S203) z3
- Salt etc. can be used.

The silver halide emulsion used in the present invention is spectrally sensitized using one or more enhancing dyes in order to impart photosensitivity in a desired wavelength range. Exacerbating pigments include cyanine pigment, merocyanine pigment, styryl pigment, hemicyanine pigment, holopolar cyanine pigment, oxonol pigment,
and hemioxonol dyes, etc. can be used. Particularly useful dyes are cyanine dyes and merocyanine dyes. As the basic heterocyclic nucleus of pigments, any nucleus commonly used for cyanine dyes can be used.

Namely, viroline nucleus, oxazole nucleus, oxazoline nucleus, thiazole nucleus, thiazoline nucleus, pyrrole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, indole nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole. Nuclei, quinoline nuclei, etc. can be applied.

The silver halide photographic light-sensitive material according to the present invention is formed by coating on a support at least one hydrophilic colloid layer containing the silver halide emulsion of the present invention, and other non-photosensitive hydrophilic colloids. Layers such as protective layers, intermediate layers, antihalation layers, filter layers, etc. may be applied. These hydrophilic colloid layers may contain inorganic or organic hardeners. Hardening agents include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds (dimethylol urea, methyloldimethylhydantoin, etc.), active halogen compounds (2,4-dichloro-6-hydroxy- 5-
) riazine, mucochloric acid, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-3-
triazine, etc.), epoxy and aziridine hardeners, and the like can be used.

The above-mentioned hydrophilic colloid layer used in the present invention may contain various photographic additives, such as emulsion stabilizers (6-hydroxy-4-methyl-1,3,3a, 7-tetrazaindene, etc.), if necessary. Zyinden compounds), spreading agents (saponins, etc.), gelatin plasticizers (acrylic acid ester copolymers, etc.), antistatic agents, coating aids, and photographic property improvements (e.g. development acceleration, high contrast). various surfactants (cationic, anionic, nonionic, amphoteric surfactants), fog suppressants (5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, etc.), capping agents, dimensions of photographic materials. Use of water-insoluble or sparingly soluble polymer latex (homo- or copolymers of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc.) for the purpose of improving temperature stability, etc., to the extent that the effects of the present invention are not impaired. I can do it.

In the present invention, photographic processing of the image-exposed photographic light-sensitive material can be carried out using known methods.

A known treatment liquid can be used. The treatment temperature is preferably in the range of 18 to 50°C.

The developer used in the present invention can contain a known developing agent. Dihydroxybenzenes (
hydroquinone, etc.), 3-pyrazolidones (1-phenyl-3-pyrazolidone, etc.), aminophenol IQ
(N-methyl-p-aminophenol, etc.), etc. can be used.

Particularly preferred are phenidone-hydroquinone (PQ) type or metho-hydroquinone (MQ) type developers containing dihydroxybenzenes and one selected from 3-pyrazolidones or aminophenols.

The developer used in the present invention has a free sulfite ion concentration of at least 0.15 mol/1.

Preferably 0.25 mol/! That's all. As a source of sulfite ions, sulfites such as sodium sulfite and potassium sulfite can be used. The developer also contains known preservatives (hydroxylamine, etc.), alkaline agents, and inorganic capri inhibitors (potassium bromide, sodium bromide, etc.).
, organic fog suppressants (5-nitroindazole, 5-methylbenzotriazole, etc.), development accelerators (alkanolamines, etc.), PTL buffers (sodium phosphate, potassium phosphate, etc.), water softeners (ethylenediaminetetraacetic acid, etc.) (sodium, etc.), surfactants, color toning agents, antifoaming agents, etc.

The pt+ of the developer according to the present invention is set in the range of 11 to 12.5. Particularly preferably, it is set in the range of 11.5 to 12.3. If the pH is lower than 11, it is difficult to achieve the contrast enhancement effect of the present invention. Also, the pH is 12
．． If it exceeds 5, even if the concentration of sulfite ions is high, the developer becomes unstable and cannot maintain stable photographic properties for more than 30 hours in normal usage.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 A silver nitrate aqueous solution and a potassium bromide aqueous solution were simultaneously added to a gelatin solution kept at 60°C while keeping the pAg at 7.0.
A monodisperse cubic silver bromide emulsion with an average grain size of 0.2 μm was prepared by adding the solution over a period of 1 minute.

After removal of the soluble salts by conventional methods, 2.5X10-' moles of sodium thiosulfate and 5X1 mole of silver bromide were added.
0-' mol of HAuC& was added and chemically aged at 60°C for 90 minutes. This emulsion contains 85 g of gelatin per mole of silver bromide. The internal sensitivity of this emulsion is negligibly low compared to the surface sensitivity, and it is essentially a surface latent image type emulsion.

This silver bromide emulsion contains 1.9 g of 6-hydroxy-4-methyl-1,3,3a,7-titrazaindene and 4.2×10-' moles of anhydro-5,5 per mole of silver bromide.
'-dichloro-9-ethyl-3,3-bis(3-sulfopropyl)oxacarbocyanine triethylammonium salt was added and
．． After adding the compound (1-10) of 0XlO-' and the compound (1) according to the present invention, the emulsion layer was coated on a polyethylene terephthalate (PET) base at a chamber length of 40 cm per 100 cm. It was protected by an overcoat layer containing l-methylol-5,5'-dimethylhydantoin as a hardening agent.

After exposing these films through a sensitometric exposure wedge, they were exposed to light using an LD-220-QT automatic processor (
(manufactured by Dainippon Screen Mfg. Co., Ltd.) with a developer having the following composition, and the photographic properties were compared.

(Developer) N-methyl-p-amine 2.0 g Phenol hemisulfate hydroquinone 40.0 g Anhydrous sodium sulfite 75.0 g Potassium bromide 3.5 g 2-diethylaminoethanol 46.8 g Ethylenediaminetetraacetic acid 1.0 g Sodium salt sodium carbonate 7.0g48
% Potassium hydroxide 70.0 g 5-Methylbenzotriazole 0.8 g Add water
11 (p[I=12.0) Results are shown in Table 2.
Shown in 3. Table 2 shows the results obtained by developing with a new solution at 38° C. for 30 seconds. Table 3 shows 100% blackened Ravid Access Film 10X12 inch 25 per day
These are the results obtained by processing a sheet for 11 days and then developing it in the same manner as in Table 2. However, in the table: - Relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 3.0 excluding fog density, and the value of sample 1 is set to 100.

・Contrast (γ) indicates the average gradient of density from 0.5 to 3.0, excluding fog density. E represents the best quality (almost no occurrence of loose particles), and E represents the worst quality. A or B
is practical, C is low quality but somehow within the practical tolerance range, and D and E are impractical.

Comparative compound table 1 1l-3 I[1-6 ■-10 Comparative compound (A) Comparative compound (B) OOH Comparative compound (C) Table 2 Comparative compound (D) Comparative compound (E) 0.06 0.04 0 .04 0.04 0.04 0.04 0.06 0.05 0.06 ノ■0.0 13.2 I7.9 15.0 22.7 20.8 11.9 10.0 9.0 / Table 3 1 125 0.08 2 105 0.04 3 104 0.04 4 108 0.04 5 90 0.05 6 90 0.06 7 150 0.08 8 127 0.10 9 90 0.06 9.0 C 13゜0A 17, OA 14.6 A 20, OB 14, OC 8, OC 9, OC 9, OB Example 2 1.2X10-3 mol of compound (II- A photographic emulsion was prepared in the same manner as in Example 1, except that 4) was used, and it was developed in the same manner.

The results are shown in Table 4.5. Table 4 shows the temperature at 38°C1 using the new solution.
These are the results obtained by developing for 30 seconds.

Table 5 is 100% blackened rabbit access film 10X1
After processing 25 2-inch pieces per day for 11 days, Table 4
These are the results obtained by developing in the same manner as above.

As is clear from Table 3, Samples Nos. 2 to 4 of the present invention show less increase in sensitivity and fog in fatigue fluids and improved pesosparity than Samples Nos. 5 to 9 (comparative samples).

Moat-1-1 Large-5 0,05 0,04 0,04 0,04 0,04 0,05 0,05 0,05 No10.0 13.0 16, O 15,5 21,0 20, O 11,0 10,0 9,5 0,0910,0 0,0412,8 0,0416,5 0,0415,0 0,0518,5 0,0617,8 0,0810,0 0,099°3 0.06 9゜0 As is clear from Table 5, Samples No. 2 to 4 of the present invention had less variation in sensitivity and fog with fatigue fluid than Samples Nos. 5 to 9 (comparative samples), and had improved Penopa. ing.

〔Effect of the invention〕

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material and a photographic image forming method that have high sensitivity and high contrast and less generation of loose particles. It is possible to provide a silver halide photographic light-sensitive material and a method for forming a photographic image in which sensitivity or gamma does not fluctuate or fog density increases even if the composition of a developer changes.

Claims (1)

[Claims] 1. Having at least one silver halide emulsion layer on a support, the emulsion layer or other hydrophilic colloid layer being represented by the following general formula (I) or (II) A negative-working silver halide photosensitive material containing at least one compound and at least one compound represented by formula (III). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, R^3 and R^4 are respectively It independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. However, this excludes the case where R^3 and R^4 are both hydrogen atoms. ] General formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z is N or CR^7 (R^7 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group),
R^5 represents an alkyl group or an aryl group substituted with one or more sulfonate groups or carboxyl groups. R
^6 represents a substituted or unsubstituted aryl group. R^8
represents a hydrogen atom or a substituted or unsubstituted alkyl group. 2. Having at least one silver halide emulsion layer on the support, and containing at least one compound represented by the following general formula (I) or (II) in the emulsion layer or other hydrophilic colloid layer. After image exposure is applied to a negative-working silver halide photosensitive material containing at least one compound represented by the general formula (III), the material contains 0.15 mol/l or more of sulfite ions and has a pH of 11 to 1. A method for forming an ultra-high contrast negative image, which comprises developing with a developer of 12.5. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, R^3 and R^4 are respectively It independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. However, this excludes the case where R^3 and R^4 are both hydrogen atoms. ] General formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z is N or CR^7 (R^7 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group),
R^5 represents an alkyl group or an aryl group substituted with one or more sulfonate groups or carboxyl groups. R
^6 represents a substituted or unsubstituted aryl group. R^8
represents a hydrogen atom or a substituted or unsubstituted alkyl group. ]