JPH06194773A - Silver halide photographic material and image forming method - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic material which is sufficiently contrasty with a developer having a pH lower than a determined value and has less black dot, and an image forming device having a good shelf life of the developer and resistant to long-term use with less replenishing quantity. CONSTITUTION:In a silver halide photographic material for treating a negative photographic material having at least one silver halide emulsion layer on a support body and also a hydrazine derivative represented by the formula on the silver halide emulsion layer or other hydrophilic colloidal layers with a developer having a pH lower than pH11.0 to form a contrasty black-and-while image, the halogen composition of the silver halide emulsion contains 5 mole % to 50 mole % of C1 as the whole, and the C1 content in the particle most outside layer is lower than the C1 contents in the particle inner part. In the formula of Ar-NHNH-(C=O)-R, R represents hydrogen atom or a blocking group, and Ar represents an aryl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and an image forming method. In addition, the present invention relates to an image forming method in which the storability of the developing solution is good, and even if the replenishing amount is small, it can withstand long-term use.

[0002]

BACKGROUND OF THE INVENTION It is known that certain silver halides can be used to form photographic images of extremely high contrast, and methods of forming such photographic images are used in the field of photolithography. For example, a lithographic silver halide light-sensitive material composed of silver chlorobromide (at least a silver chloride content of 50 mol% or more) is well known in the art.
In principle, the concentration of sulfurous acid cannot be increased, and there is a drawback that it is unstable to air oxidation.

For this reason, the instability of the image forming method by the developing method (lith development system) as described above is eliminated, and the image is developed with a processing solution having good storage stability, and an image having super high contrast photographic characteristics can be obtained. A forming system is desired, and U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857, 4,224,401, 4,243,739, 4, No. 272,606, No. 4,311,781, surface latent image type silver halide photographic light-sensitive materials to which a specific hydrazine compound is added are added, and a sulfite preservative is added at a pH of 11.0 to 12.3. .1
A system has been proposed which forms a super-high contrast negative image having a γ of more than 10 by processing with a developer containing 5 mol / l or more and having good storage stability. However, in this new image forming system, since the pH of the developer is high, it is easily affected by air oxidation and the storability of the developer is not sufficient. Especially in recent years, with increasing environmental problems, we are trying to reduce the amount of waste liquid of processing agents as much as possible, but with the conventional hydrazine compounds that cause a high contrast at pH 11 or above, the storability of the developer is insufficient, so there is a limit to reducing the amount of waste liquid. was there. Therefore, JP-A-4-229553, JP-A-2-120736,
PH 11 as seen in JP-A-63-124045
An example is known in which a hydrazine compound having a high contrast-adjusting ability is used even in the following developing solutions. However, when developing with a developer having a pH of 11 or less, the activity of the developer is weak. Therefore, compared with the conventional system, a sufficient amount of hydrazine compound cannot be used to obtain sufficient contrast-improving ability, or the sensitivity changes due to pH changes. It had the drawback of being large. Further, there is a drawback that a failure called "black spot" in the art is likely to occur by using a large amount of hydrazine compound.

[0004]

DISCLOSURE OF THE INVENTION The object of the present invention is to
Providing a silver halide photographic light-sensitive material having a sufficiently high contrast with a developing solution of 11.0 or less and having little black spots, and an image forming system having good storage stability of the developing solution and capable of withstanding long-term use even with a small replenishing amount Is provided.

[0005]

A silver halide photographic light-sensitive material which achieves the above object of the present invention has at least one silver halide emulsion layer on a support, and the silver halide emulsion layer or another silver halide emulsion layer is provided. A negative type photosensitive material having a hydrazine derivative represented by the following general formula [I] in a hydrophilic colloid layer is added.
In a silver halide photographic light-sensitive material which is processed with a developing solution of H11.0 or less to form a black and white image having high contrast, the halogen composition of the silver halide emulsion as a whole is 5 mol% Cl.
The content of Cl is 50 mol% or less and the Cl content of the outermost layer of the particles is lower than the Cl content of the inside of the particles.

Further, the image forming method of the present invention which achieves the above object has at least one silver halide emulsion layer on a support, and the silver halide emulsion layer or another hydrophilic colloid layer has the following general composition. The silver halide emulsion has a hydrazine derivative represented by the formula [I], the total halogen composition of the silver halide emulsion is 5 mol% or more and 50 mol% or less, and the Cl content of the outermost layer of the grain is inside the grain. The negative photosensitive material having a Cl content of less than 1 is treated with a developer having a pH of 11.0 or less to form a hard black and white image. General formula [I] Ar-NHNH- (C = O) -R In the formula, R is a hydrogen atom or a blocking group, and specifically, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, It represents a carbamoyl group or an oxycarbonyl group. Ar represents an aryl group. In the present specification, “%” of the halogen composition indicates “mol%”. same as below.

The silver halide emulsion grains used in the present invention can have a plurality of layers having different compositions.
In a preferred embodiment, the outermost layer preferably has a low Cl content, and I may be contained in the outermost layer. In a particularly preferred embodiment, the halogen composition outside 80% of the final particle size is 15% or less of Cl, and particularly preferably C
l 5% or less. The halogen composition inside 80% of the final grain size is Cl 10% or more and 80% or less, and particularly preferably 20% or more and 50% or less. The average grain size of the silver halide grains is preferably 0.05 to 0.5 μm, more preferably 0.10 to 0.40 μm.

A preferred hydrazine derivative used in the present invention is represented by the general formula [I], more preferably the general formula [II]. General formula [I] Ar-NHNH- (C = O) -R In the formula, R is a hydrogen atom or a blocking group, and Ar is
Represents an aryl group.

[0009]

[Chemical 1]

In the formula, R represents a hydrogen atom or a blocking group, and specifically represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group. R ₁ represents a substituent.
Further, R ₁ preferably has a diffusion resistance or a silver halide adsorption group. Specific examples thereof include compounds described in the following patent-related documents. JP-A-2-37, 2-84
No. 1, No. 2-947, No. 3-125434, No. 3-
No. 240036, No. 3-259240, Japanese Patent Application No. 3-2
87997, 3-3-307934, 3-3219.
No. 88, No. 3-345207, No. 3-345817.
Nos. 3,345,819, 3,345,820, 3,316796, 3,345,818 and 4-1.
No. 0268, No. 4-13218, No. 4-21322 and the like. More specific examples include the following hydrazine compounds.

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

At least one of the hydrazine compounds of the present invention is 5 × 10 ^{−7 to} 5 × per mol of silver halide.
It is preferable to add 10 ⁻¹ mol, particularly 5 × 10 ⁻⁶ to 1 × 10 ⁻² mol. The hydrazine compound of the present invention,
When it is contained in a layer other than the silver halide emulsion layer, it is preferably contained in a layer adjacent to the silver halide emulsion layer.

In the present invention, it is preferable to use a nucleation accelerator. Examples of the nucleation accelerator used in the present invention include amine compounds, hydrazine compounds other than the above, quaternary onium salt compounds, carbinol compounds, and the like.
Amine compounds and carbinol compounds are preferred. These nucleation accelerators are disclosed in JP-A-4-56749 and JP-A-6-6749.
Those described in Nos. 3-124045 and 62-187340 are mentioned. These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule. Other specific examples include the compounds described in the following patent-related documents. Japanese Patent Application Nos. 3-295926 and 3-2
No. 93366, No. 3-286619, No. 4-3345.
No. 1 and the like. More specifically, the following nucleation accelerators are listed, but the present invention is not limited thereto. As a compound described in JP-A-4-56949

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

And the like. For example, in the silver halide photographic emulsion and backing layer used in the present invention, various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, ultraviolet rays, etc. Absorbents, anti-irradiation dyes, heavy metals, matting agents and the like can be further incorporated by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer of the present invention.

As a support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, and polyolefin are coated. paper,
Examples thereof include glass and metal. These supports are subjected to an undercoat or an undercoating process, if necessary. These additives are described in more detail in Research Disclosure Vol. 176 Item / 7643 (December 1978) and Vol. 187 Item / 8716 (November 1979).
And the description can be referred to in the present invention.

The present invention will be further described. The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer. That is, the silver halide emulsion layer is
At least one layer may be provided on one side of the support, or at least one layer may be provided on both sides of the support. The silver halide emulsion can be coated directly on the support or can be coated through another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the emulsion layer. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, you may provide the intermediate layer which consists of hydrophilic colloids as needed. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer and a backing layer may be provided between the silver halide emulsion layer and the protective layer.

Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described. As the silver halide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide, particularly silver chlorobromide, are preferable. The average grain size of the silver halide grains is preferably in the range of 0.05 to 0.5 [mu] m, and more preferably 0.10 to 0.40 [mu] m. The grain size distribution of the silver halide grains is arbitrary, but the monodispersity index value defined below is preferably 1 to 30, and more preferably 5 to 20. Where the monodispersity is
It is defined as a value obtained by multiplying the value obtained by dividing the standard deviation of particle diameter by the average particle diameter by 100. For the sake of convenience, the grain size of silver halide grains is represented by the edge length in the case of cubic grains, and the other grains (octahedral, tetradecahedral, etc.) are calculated by the square root of the projected area.

When the present invention is carried out, for example, silver halide grains having a multi-layered structure of at least two layers can be used. For example, silver chlorobromide in the core portion and shell portion can be used. It is preferable to use silver chlorobromide grains in which is silver bromide or silver chlorobromide. At this time, iodine can be contained in any layer within 5%. The silver halide grains used in the silver halide emulsion have a cadmium salt, a zinc salt, a lead salt, at least one of a grain forming process and a growing process.
A metal ion is added using at least one selected from thallium salt, iridium salt (complex salt containing), rhodium salt (complex salt containing), and iron salt (complex salt containing iron), and at least one of inside or on the surface of the particle is added. The metal sensitizer can be contained in the part, and the reduction sensitizer can be added to the inside of the grain or at least a part of the grain surface by placing in a suitable reducing atmosphere.

Further, the silver halide can be sensitized with various chemical sensitizers. Examples of the sensitizer include active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiacinate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.). ), A reduction sensitizer (triethylenetetramine,
Stannous chloride, etc.), such as potassium chloroaurite,
Various noble metal sensitizers typified by potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc., alone or Two or more kinds can be used in combination. When a gold sensitizer is used, rodan ammon can be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains having a surface sensitivity higher than the internal sensitivity, that is, silver halide grains giving a so-called negative image. Performance can be improved. The silver halide emulsion used in the present invention includes mercaptos (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole) and benzotriazoles (5-bromobenzotriazole-5-).
Methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), indazoles (5-nitroindazole) and the like can be used for stabilization or fog suppression.

The photosensitive silver halide emulsion layer or its adjacent layer is provided with Research Disclosure (Research) for the purpose of increasing sensitivity, increasing contrast or promoting development.
Disclosure) No. 17463 XXI term B
~ The compounds described in the section D can be added. A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide emulsion.

Next, the processing method of the silver halide photographic light-sensitive material of the present invention will be described. The main processing steps adopted in such a processing method are composed by appropriately combining development, fixing, washing, stabilizing, etc., for example, development → fixing → washing, developing → fixing → stable, developing → fixing → washing → stable. Etc. In the present invention, the developing time is not particularly limited, but is preferably 10 seconds or less.

In the present invention, the total processing time of developing, fixing, washing with water, stabilizing and drying is preferably within 45 seconds. In this case, the film includes the transfer time from the developing solution to the fixing solution and from the fixing solution to the washing solution (stabilizing solution). For example, the following developing agents are used in the development processing liquid. HO- (C
Typical examples of (H = CH) n-OH type developing agents include hydroquinone, and catechol and pyrogallol. In addition, HO- (CH = CH) n-N
Typical H ₂ type developers are ortho and para aminophenols or aminopyrazolones, such as N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol and p-hydroxyphenylamino. There are acetic acid, 2-aminonaphthol and the like.

Heterocyclic type developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-.
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
Examples thereof include 3-pyrazolidones such as 4-methyl-4-hydroxymethyl-3-pyrazolidone.

In addition, T. H. James, The Theory of the Photographic Process, 4th Edition (The Theory of the Photog)
radical Process, Fourth Ed
pp. 291-334 and the Journal of the American Chemical Society.
al of the American Chemical
al Society) Vol. 73, p. 3,100 (1
The developing agents described in 951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination.

Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material of the present invention, the effect of the present invention is not impaired. Further, hydroxylamine or a hydrazide compound may be used as a preservative. In addition, it is possible to adjust the pH with a caustic alkali, an alkali carbonate, an amine or the like as used in a general black-and-white developer and to have a buffer function. The developer used in the present invention has a pH of 11.
The feature is that those of 0 or less can be used.

Further, the developing solution contains an inorganic development inhibitor such as bromcali, 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine,
Organic development inhibitors such as guanine and 1-phenyl-5-mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxides, sodium alkylaryl sulfonates, natural It is optional to add a surface active agent such as saponin, saccharide or alkyl ester of the above compound, a hardening agent such as glutaraldehyde, formalin and glyoxaza, and an ionic strength adjusting agent such as sodium sulfate. The developer used in the invention preferably contains no amine compound when the emulsion contains an amine compound or a quaternary onium salt.

[0035]

EXAMPLES The present invention will be illustrated below with reference to examples. Example 1

[0036]

[Table 1]

[0037]

[Table 2]

Using the controlled double jet method, solutions B and C were added over 70 minutes to solution A maintained at 60 ° C. in the combinations shown in Table 3. During this period pAg =
The core was controlled to have a mean particle size of 0.16 μm. Immediately after obtaining the core, the solutions D and E of the combination shown in Table 3 were added in the same manner, and 6 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver immediately before the completion of grain formation. The liquid D and the temperature were controlled so that the temperature was 60 ° C. and pAg = 7.2, and they were mixed so as to form a cube having a final particle size of 0.20 μm.

After the completion of mixing, the product was washed with water by a usual flocculation method, added with Gel and redispersed to give a final particle size of 0.20.
μm, cubic Em1-9 were obtained.

[0040]

[Table 3]

(Preparation of silver halide photographic light-sensitive material) An undercoat layer having a thickness of 0.1 μm is formed on a screen (Japanese Patent Laid-Open No. 59-19941).
No. 1) of 100 μm thick on one undercoat layer of each of the above Em1 to 9 and a silver halide emulsion layer of the following formulation (1) with a gelatin amount of 2.0 g. / M ² , and the amount of silver was 3.2 g / m ^2, and a protective layer of the following formulation (2) was further applied thereon so that the amount of gelatin was 1 g / m ² . On the other undercoat layer on the opposite side, a backing layer is coated according to the following prescription (3) so that the amount of gelatin is 2.4 g / m ^2, and the protection of the following prescription (4) is further applied thereon. A sample was obtained by coating the layer so that the amount of gelatin was 1.0 g / m ² .

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion Silver amount 3.2 g / m ² Antifoggant: 5-nitroindazole 10 mg / m ² : 1-phenyl mercaptotetrazole 2 mg / m ² stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7- tetrazaindene Ten 30 mg / m ² hydrazine derivative (shown in Table 1) nucleation accelerator (18) 60 mg / m ² Surfactant: sodium dodecylbenzene sulfonate 0.1 g / m ² sodium sulfosuccinate isopentyl normal decyl ester 8.0 mg / m ² Sensitizing dye: anhydro-5,5′-dichloro-9-butyl- 3,3 ′ bis (3-sulfopropyl) oxocarbocyanine hydroxy sodium salt 8.0 mg / m ² polyethylene glycol content Molecular weight 4000 30 mg / m ² latex polymer:

[0043]

[Chemical 10]

Hardener: 2-hydroxy-4,6-dichloro-1,3,5-triazine 60 mg / m ²

Formulation (2) (Emulsion protective layer composition) Gelatin 0.9 g / m ² Matting agent: Silica having an average particle size of 3.5 μm 10 mg / m ² Surfactant: Sodium sulfosuccinate-di (2-ethylhexyl) ester 10 mg / m ² Hardener: Formalin 30 mg / m ²

Formulation (3) (backing layer composition)

[0047]

[Chemical 11]

Gelatin 2.4 g / m ² Surfactant: sodium dodecylbenzene sulfonate 0.1 g / m ² sodium sulfosuccinate isopentyl normal decyl ester 6.0 mg / m ²

Formulation (4) (Composition of backing protective layer) Gelatin 1 g / m ² matting agent: polymethylmethacrylate having an average particle size of 3.0 to 5.0 μm 50 mg / m ² Surfactant: sodium sulfosuccinate, di (2) -Ethylhexyl) ester 10 mg / m ² Hardener: Glyoxal 25 mg / m ² 2-Hydroxy-4,6-dichloro-1,3,5-triazine 35 mg / m ² Quality test of the obtained sample according to the following test method Then, the sample was evaluated. The results are shown in Table 4.

(Black Pot Quality Test Method) Sample No. 1 to
The undeveloped sample No. 24 was subjected to development processing under the following conditions with the following automatic processor for rapid processing, in which a developing solution having the following developing solution formulation and a fixing solution having the following fixing solution formulation were added. Observe the halftone dots with a magnifying glass of 100 times, and assign the highest rank "5" to those that have no black spots in the halftone dots, and rank "4" according to the degree of occurrence of black spots in the halftone dots. ,
The ranks of “3”, “2”, and “1” were sequentially lowered and evaluated. In the ranks "1" and "2", black spots are large, which is a level unfavorable for practical use.

(Sensitivity Test Method) The obtained sample was exposed, developed and fixed under the following condition (I) to determine the sensitivity. (I): The obtained sample was brought into close contact with a step wedge, and 3
Immediately after exposing to a tungsten light of 200 ° K for 3 seconds, processing was performed under the following conditions with an automatic developing machine GR-26SR (manufactured by Konica) in which a developing solution and a fixing solution having the compositions shown below were charged. The sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives the fog density + 3.0 density. The sensitivity of 18 was expressed as 100. <Γ: Gamma> It was obtained from the slope of the characteristic curve in transmission densities 1 to 3.

<Processing Conditions> The processing conditions are as follows. [Developer formulation] Sodium sulfite 50g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1g Diethylenetriamine pentaacetic acid 1.5g Boric acid 2g Potassium bromide 5g Potassium carbonate 30g 5-Methylbenztriazole 0.3g 2 -Mercaptobenzthiazole 0.02 g Hydroquinone 25 g Potassium hydroxide Amount to bring the pH of the working solution to the pH shown in Table 4 At the time of use, water was added to make 1 liter.

In order to examine the stability of the developing solution, 50 l of the developing solution was placed in a poly container having an opening area of 3000 cm ² and allowed to stand for 5 days while being freely exposed to air (old developing solution).

[Fixing liquid formulation] Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50 % W / V aqueous solution) 15.7 g Gluconic acid (50% W / W aqueous solution) 8.55 g Aluminum sulfate (48% W / W aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid Amount to bring the pH of the used solution to 4.6 Water was added to make 1 liter.

[Development processing conditions] Process Temperature Time Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Washing with water Normal temperature 15 seconds Drying 40 ° C. 15 seconds

[0056]

[Table 4]

Example 2 No. 1 of Example 1. 10 and No. A running test was performed under the following conditions using each of 18 samples. Blackening rate 80% Number of processed sheets: 100 sheets / 1 day 5 days processing Developer: New developer prescription of Example 1 Developer: Dainippon Screen LD-281Q Developer When running started under these conditions And at the end, the sensitivity and the black spot were examined by the same method as shown in Example 1.

[0058]

[Table 5]

[0059]

EFFECTS OF THE INVENTION Provided is a silver halide light-sensitive material which has a sufficiently high contrast with a developer having a pH of 11.0 or less and has few black spots, has a good storability of the developer and can withstand long-term use even if the replenishing amount is small. An image forming system can be provided.

Claims (3)

[Claims] 1. A negative having at least one silver halide emulsion layer on a support and having a hydrazine derivative represented by the following general formula [I] in the silver halide emulsion layer or another hydrophilic colloid layer. In a silver halide photographic light-sensitive material which forms a black and white image with high contrast by processing a light-sensitive light-sensitive material with a developer having a pH of 11.0 or less, the total halogen composition of the silver halide emulsion is 5 mol% or more and 50 mol% or more. %, And the content of Cl in the outermost layer of the grain is lower than the content of Cl in the interior of the grain. General formula [I] Ar-NHNH- (C = O) -R In the formula, R is a hydrogen atom or a blocking group, and Ar is
Represents an aryl group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the halogen composition of the outermost layer of the grains is 15 mol% or less of Cl. 3. A support having at least one silver halide emulsion layer, and the silver halide emulsion layer or another hydrophilic colloid layer having a hydrazine derivative represented by the following general formula [I]. The total silver halide composition of the silver halide emulsion is 5 mol% or more and 50 mol% or less, and the outermost layer of the grains has a Cl content lower than the Cl content inside the grains. An image forming method characterized by forming a black and white image with high contrast by processing with a developing solution of 0.0 or less. General formula [I] Ar-NHNH- (C = O) -R In the formula, R is a hydrogen atom or a blocking group, and Ar is
Represents an aryl group.