JPH05197091A - Image forming method - Google Patents

Abstract

PURPOSE:To provide an image forming method possible to attain the photographic property of extremely high contrast negative gradation free from unevenness of development or sand fogging by using a stable developer made from a novel hydrazine derivative. CONSTITUTION:A silver halide photographic sensitive material is developed in the presence of the hydrazine derivative expressed by the formula. In the formula, each of A1 and A2 is 2-valent aromatic group or heterocyclic group, each of G1 and G2 is carbonyl group, sulfonyl group, oxalyl group, or phospholyl group, each of Z1 and A2 is hydrogen atom, hydroxyl group, alkyl group, aryl group, aralkyl group, alkoxyl group, aryloxy group, amino group or an adsorption accelerating group to silver halide and each of L1, L2 and R is 2-valent organic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material which gives a very hard negative image, a highly sensitive negative image and a good halftone image quality.

[0002]

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,
No. 727 (developer in which ascorbic acid and hydrazine are combined), No. 3,227,552 (hydrazine is used as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831. No. 2 (containing β-monophenyl hydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers), No. 2,419,975, and "The Theory of Photographic process" by Mees.
The third edition (1966), page 281 and the like.

Among these, especially US Pat. No. 2,41
No. 9,975, it is disclosed to obtain a hard negative image by adding a hydrazine compound. That is, when a hydrazine compound is added to a silver chlorobromide emulsion and development is performed with a developing solution having a high pH such as 12.8, a gamma (γ) of more than 10 and extremely high contrast photographic characteristics can be obtained.
Have been described. However, a strong alkaline developer having a pH close to 13 is easily oxidized by air, is unstable, and cannot withstand long-term storage or use. The ultra-high contrast photographic characteristics with a gamma value of more than 10 are very useful for the photographic reproduction of continuous-tone images by dot image, which is useful for printing plate making, or the reproduction of line drawings, whether it is a negative image or a positive image. Is.

For this purpose, conventionally, a silver chlorobromide emulsion having a silver chloride content of more than 50 mol%, preferably more than 75 mol%, has been used, and the effective concentration of sulfite ion is extremely low (usually). A method of developing with a hydroquinone developer (0.1 mol / l or less) was generally used (lith development). However, in this method, since the sulfite ion in the developing solution is low, the developing solution is extremely unstable and cannot be stored for more than 3 days. Furthermore, since none of these methods requires the use of a silver chlorobromide emulsion having a relatively high silver chloride content, high sensitivity cannot be obtained. Therefore, there has been a strong demand for obtaining ultrahigh contrast photographic characteristics useful for reproducing halftone images and line images by using a high-sensitivity emulsion and a stable developing solution.

To this end, US Pat. No. 4,168,
977, 4,224,401, 4,243,7
No. 39, No. 4,269,929, No. 4,272,61
No. 4, 4,323,643 and the like disclose silver halide photographic light-sensitive materials which give extremely hard negative photographic characteristics by using a stable developing solution. Acylhydrazine compounds used therein Have been found to have some drawbacks. That is, these hydrazines are known to generate nitrogen gas during the development process, and this gas collects in the film to form bubbles,
May damage the photographic image. Therefore, a compound capable of obtaining extremely hard photographic characteristics even with a small addition amount has been desired in view of reducing the generation of bubbles and simultaneously reducing the cost for producing a light-sensitive material. Further, if development is continued using these hydrazines, countless circular fog (sand fog) tends to occur in the unexposed portion, and the image quality is significantly impaired.

Further, conventional hydrazines are required in a large amount for increasing the sensitizing contrast, and when it is required that the sensitivity of the photosensitive material is particularly high, another sensitizing technique ( For example, increase chemical sensitization; increase grain size;
US Pat. Nos. 4,272,606 and 4,241,16
It is desirable to use in combination with a compound which promotes sensitization as shown in No. 4), but when these sensitization techniques are used together, sensitization with time and fog during storage generally occur. There is. Furthermore, when development is performed using conventional hydrazines, so-called development unevenness easily occurs due to uneven stirring of the developer. This development unevenness is remarkable in the developing machine processing, and if the development processing is strengthened in order to eliminate this development unevenness, the above-described sand fog development occurs. Therefore, there has been a demand for a compound which does not have the problems of stability with time, uneven development and sand fog as described above, is effective even when added in a very small amount, and is easy to synthesize.

[0007]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a photographic characteristic of an extremely hard negative tone with a gamma of more than 10 by using a stable developing solution. To provide the material.

Secondly, the object of the present invention is to provide a negative-working silver halide photographic light-sensitive material containing hydrazines which can give good image quality without problems such as uneven development and sand fog. ..

Thirdly, an object of the present invention is to provide a negative-working type containing a hydrazine compound capable of imparting desired photographic characteristics of extremely hard negative gradation with a small addition amount without adversely affecting photographic performance. The object is to provide a silver halide photographic light-sensitive material.

Fourthly, the object of the present invention is to add hydrazines to the development processing solution, which have good processing stability (for example, no development unevenness, sand fog, etc.) and which can give photographic characteristics of rapid high contrast. By doing so, it is intended to provide a method for developing a silver halide photographic light-sensitive material in high contrast.

[0011]

The objects of the present invention have been achieved by developing a silver halide photographic light-sensitive material in the presence of a compound represented by Chemical formula 1.

(In the formula, A ₁ and A ₂ are divalent aromatic groups and heterocyclic groups, G ₁ and G ₂ are carbonyl groups, sulfonyl groups, oxalyl groups and phosphoryl groups, and Z ₁ and Z ₂ are Hydrogen atom, hydroxy group, alkyl group, aryl group, aralkyl group,
It represents an alkoxy group, an aryloxy group, an amino group or an adsorption promoting group to silver halide, and L ₁ , L ₂ and R represent a divalent organic group. )

Next, the chemical formula 1 will be described in detail. In the chemical formula ₁ , the divalent aromatic groups represented by A ₁ and A ₂ may be the same or different and each is a monocyclic or bicyclic aryl group, and examples thereof include a phenylene group and a naphthylene group.
The divalent heterocyclic groups represented by A ₁ and A ₂ may be the same or different and are 3- to 10-membered saturated or unsaturated heterocycles containing at least one of N, O or S atoms. These may be a monocycle or may form a condensed ring with another aromatic ring or a heterocycle. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and for example, a group containing a pyridylene, imidazolylene, quinolylene, benzimidazolylene, pyrimidylene, pyrazolylene, isoquinolylene, thiazolylene or benzthiazolylene group is preferable. A ₁ and A ₂ may be substituted with a substituent. As the substituent, an alkyl group, an aralkyl group, an alkoxy group, an aryl group, a substituted amino group,
Examples thereof include a hydroxy group, a sulfo group, a carboxy group, a halogen atom such as chlorine and bromine, and a cyano group. An aromatic group is preferable as A ₁ and A ₂ , and a phenylene group is more preferable.

Z ₁ and Z ₂ may be the same or different,
Preferably, when G ₁ and G ₂ are carbonyl groups, a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.), aralkyl group (eg, o-Hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, etc.), adsorption promoting group to silver halide, and hydrogen atom is particularly preferable. Preferred examples of the adsorption accelerating group to silver halide are a mercapto group, a group having a disulfide bond, or 5 to 6
Membered nitrogen-containing heterocyclic group (for example, 5-mercapto-1-phenyltetrazole, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, bezothiazole, etc.). When G ₁ and G ₂ are sulfonyl groups, Z ₁ and Z ₂ are alkyl groups (such as methyl group) and aralkyl groups (such as ο
-Hydroxybenzyl group), aryl group (eg phenyl group), substituted amino group (eg dimethylamino group) or adsorption promoting group to silver halide (eg as described above) is preferred. When G ₁ and G ₂ are oxalyl groups, Z ₁ and Z ₂ are hydroxy group, alkyl group (eg, methyl group), aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group) , An amino group or a substituted amino group {for example, 3-hydroxypropylamino group, 2,3-dihydroxypropylamino group, ο-hydroxyanilino group, ο-hydroxymethylanilino group, 4- (2,2,4,4) -Tetramethylpiperidyl) amino group or the like} or an adsorption promoting group to silver halide (for example, as described above) is preferable.
When G ₁ and G ₂ are phosphoryl groups, Z ₁ and Z ₂ are methoxy group, ethoxy group, butoxy group, phenoxy group,
A phenyl group is preferable, and a phenoxy group is particularly preferable.

L ₁ and L ₂ may be the same or different 2
Valent linking group which is alkylene, arylene, divalent heterocyclic group, -O-, -S-, imino, -COO-, -C
ONH-, -NHCONH-, -NHCOO-, -SO
_{2 NH -, - CO -,} - SO 2 -, - SO -, - NHSO 2 NH -, -
Examples thereof include NHCSNH-, -NH- and the like, and composites thereof. R is alkylene, arylene (for example, ethylene group, butylene group, dodecylene group, phenylene group, etc.), divalent group adsorbed on silver halide {for example, (5-mercaptotetrazolyl) phenylene group, etc.},
It represents a divalent heterocyclic group and may be combined with the divalent linking group described for L ₁ and L ₂ . Specific examples of the compound of the present invention are shown below, but the invention is not limited thereto.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

[0035]

[Chemical 21]

[0036]

[Chemical formula 22]

[0037]

[Chemical formula 23]

[0038]

[Chemical formula 24]

Synthesis Example 1 Synthesis of Chemical Formula 3 2.72 g of 1-formyl-2- (4-phenoxycarbonylaminophenyl) hydrazine and 1.0 g of 1,12-diaminododecane were added to 100 ml of 1,4-dioxane and heated under reflux. I went for 4 hours. After allowing to cool, the precipitated crystals were collected by filtration, washed with 1,4-dioxane, washed with methanol and dried to obtain 2.1 g of the desired product. Melting point 213-215 [deg.] C.

Synthesis Example 2 Synthesis of Chemical Formula 4 1-Bis (3-aminopropyl) -3- (2,4-di-
t-amylphenoxy) propylamine 4.06 g and 1
-Formyl-2- (4-phenoxycarbonylaminophenyl) hydrazine (5.43 g) in 1,4-dioxane 2
It was added to 00 ml and heated under reflux for 4 hours. After cooling, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, and then purified by silica gel chromatography (developing solvent: CHCl.
₃ / MeOH = 10/1) to obtain 1.85 g of the desired product. Melting point 115 ° C (softening).

Synthesis Example 3 Synthesis of Compound 13 1- (4-phenoxycarbonylaminophenyl) -2
-[(2,3-Dihydroxypropyl) aminooxalyl] hydrazine (5.30 g) and ethylene glycol bis (3-aminopropyl) ether (1.20 g) were added to 1,4-
The mixture was added to 100 ml of dioxane and heated under reflux for 3 hours.
After cooling, the precipitated crystals were collected by filtration, washed with 1,4-dioxane, washed with methanol and dried to obtain 4.5 g of the desired product. Melting point 213 [deg.] C. (dec.).

In the light-sensitive material of the present invention, the compound represented by Chemical formula 1 is preferably contained in the surface latent image type silver halide emulsion layer, but the hydrophilic property adjacent to the surface latent image type silver halide emulsion layer is preferable. It may be contained in the colloid layer. Such a layer has any function as long as it does not prevent the compound represented by Chemical formula 1 from diffusing into silver halide grains, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer and an antihalation layer. It may be a layer. Since the content of the compound of the present invention in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range, but the surface latent image Type silver halide emulsion, about 1 × 10 ⁻⁶ to 1 × 10 per mol of silver
A range of ^-2 moles is practically useful.

When the hydrazine compound represented by Chemical formula 1 used in the present invention is mixed in the developer, it is 10 ^-6.
10 ^-1 mol / l is suitable, and more preferably 5 x 1
A range of 0 ^{-5 to} 5 × 10 ^-2 mol / l is particularly preferable.

The silver halide used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, and silver chloride, silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide. Etc. can be used, but when silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is preferably 5 mol% or less. The form, crystal habit, size distribution, etc. of the silver halide grains are not particularly limited, but those having a grain size of 0.7 micron or less are preferable.

The silver halide emulsion includes a sulfur compound which reacts with a gold compound such as chloroauric acid salt or gold trichloride, a salt of a noble metal such as rhodium or iridium or a silver salt to form silver sulfide, and a first compound. The sensitivity can be increased with a reducing substance such as a tin salt or amines without coarsening the particles. Further, an iron compound such as a salt of a noble metal such as rhodium or iridium or a red blood salt may be allowed to be present during physical ripening or nucleation of silver halide grains. In particular, addition of a rhodium salt or a complex salt thereof is preferable because it further promotes the effect of the present invention of achieving photographic characteristics of ultrahigh contrast in a short developing time.

In the present invention, the surface latent image type silver halide emulsion means an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. No. 4,224,224. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of No. 401. It is desirable that the silver halide emulsion be monodisperse, and in particular, the above-mentioned US Pat.
An emulsion having the monodispersity defined in No. 224,401 is preferable.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
Cyanine dyes, merocyanine dyes, and composite merocyanine dyes. These sensitizing dyes may be used alone or in combination.
A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, 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 sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. It is possible to use various kinds of synthetic hydrophilic polymer substances such as partial acetals of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and other single or copolymers. .. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, an enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. .. That is, azoles,
For example, benzothiazolium salt, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles; mercaptopyrimidines, mercaptotriazines, thioketo compounds; azaindenes, etc. Many compounds known in the art as antifoggants or stabilizers can be added. Among these, particularly preferred are benzotriazoles (eg 5-methylbenzotriazoles) and nitroindazoles (eg 5-methylbenzotriazoles).
Nitroindazole). These compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chrome alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-). 6-
Hydroxy-S-triazine etc.) and the like can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may include a coating aid, an antistatic agent, a slipperiness improving agent, an emulsion dispersion agent, an adhesion preventing agent and a photographic characteristic improving agent (for example, development). A surfactant may be included for various purposes such as acceleration, hardening, and sensitization. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulfates,
Anionic surfactants containing acidic groups such as carboxyl groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups such as alkyl phosphoric acid esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or Amphoteric surfactants such as phosphates; aliphatic or aromatic quaternary ammonium salts, pyridinium,
Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid,
A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing sufficient sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Especially 10.5-1
With the developer of 2.3, a super-high contrast negative image can be sufficiently obtained.

The developing agent that can be used in the method of the present invention is not particularly limited, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination.

Other developers include pH buffers such as alkali metal sulfites, carbonates, borates and phosphates, bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles). Or a development inhibitor or antifoggant, such as benzotriazoles). Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a film hardener, a film silver stain inhibitor (for example, 2-mercaptobenzimidazole acids), etc. May be included. Specific examples of these additives are Research Disclosure 17
No. 6, 17643, etc.

As the fixing liquid, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used.
Further, the fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

In the present invention, a system may be adopted in which a developing agent is incorporated in a light-sensitive material and processing is performed with an alkaline activator solution. (JP-A-57-129436, 57-129433, 57-129434, 5)
7-129435, U.S. Pat. No. 4,323,643, etc.). The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. It is preferable to use an automatic processor for photographic processing. In the present invention, even if the total processing time from putting the light-sensitive material into the automatic developing machine until it comes out is set to 60 seconds to 120 seconds, a sufficiently high-hardness negative tone photographic characteristic can be obtained.

[0058]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A silver iodobromide emulsion composed of cubic crystals containing 97 mol% AgBr and 3 mol% AgI and having an average particle size of 0.25 micron was prepared by the double jet method, washed with water and re-used by a conventional method. After dissolution, it was chemically sensitized with sodium thiosulfate. This silver iodobromide emulsion was divided into 13 parts, and then the compounds of the formula 1, formula 3, formula 9, formula 20, and formula 23 of the present invention and the following comparative compounds, formula 25 and formula 26 are shown in Table 1. Then, the amount of silver was 3.7 g per 1 m ² on the polyester film. The film sample thus prepared was subjected to wedge exposure and then developed at 20 ° C. for 1 to 5 minutes using a developer having the composition shown below.

[0060]

[Chemical 25]

[0061]

[Chemical formula 26]

[0062]

[Chemical 27]

<Developer> Hydroquinone 30 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-plaseridone 0.3 g Sodium sulfite 75 g EDTA.2Na 1.0 g Tripotassium phosphate 80 g Potassium bromide 2. 0 g NaOH 13 g 5-Methylbenzotriazole 0.3 g 1-Diethylamino-2,3-diethylpropoxypropane 17 g Water is added and the pH is adjusted to 11.5 with 1 l potassium hydroxide. The results are shown in Table 1.

[0064]

[Table 1]

A) The addition amount is shown by the number of moles per 1 mole of silver. b) The exposure required to give a density of 1.0 is expressed as relative sensitivity. (The sensitivity when the sample of film No. 1 was developed for 3 minutes was 10.0.) C) The average gradient from density 0.5 to 2.0 is expressed as gamma.

As is clear from Table 1, the compounds of the present invention are
Compared with the comparative compound, it was found that the photographic characteristics with high contrast were almost completed even in the development processing at 20 ° C. for 1 minute, and that the fog did not increase even after the development for a long time. The effect is obvious. I am trying. The effectiveness of the compound of the present invention having the structure represented by Chemical formula 1 is recognized. Furthermore, since the change in sensitivity due to the change in development time is extremely small compared to the comparative compound, it can be seen that the stability against development is also high.

Further, when the unexposed portion of each sample after the development processing was examined, it was found that the sample to which the comparative compound was added (No. 2).
In Nos. 7 to 7), a clear sand fog was already generated at the development time of 3 minutes, but no sand fog was observed in the samples (Nos. 8 to 15) to which the compound of the present invention was added.

Example 2 Next, a part of the film sample obtained in Example 1 was heated at 40 ° C. for 3 hours.
After heating for 0 days, exposure and development (2
(0 ° C. for 3 minutes), and the sensitivity and fog value immediately after coating were compared. The results are shown in Table 2.

[0069]

[Table 2]

As is clear from Table 2, the compounds of the present invention show very little change in sensitivity and increase in fog with storage.

Example 3 Next, another half of the film sample obtained in Example 1 was tested for dot quality. That is, after exposing each film sample through a sensitometric exposure wedge using a 150-line gray contact screen,
The same developer as before was developed at 38 ° C. for 30 seconds, and the halftone dot quality was observed. The results are shown in Table 3.

The halftone dot quality was visually evaluated on a scale of 5, with 5 being the best and 1 being the worst. As the halftone dot original plate for plate making, 5 and 4 are practical, 3 is poor, but it can be used barely, and 2 and 1 are practically unusable qualities.

[0073]

[Table 3]

As is clear from Table 3, the compounds of the present invention show good halftone dot quality.

[0075]

According to the image forming method of the present invention, there is no problem of development unevenness and sand fog, and a stable developer can be used to obtain photographic characteristics of extremely high tone gradation with a gamma of more than 10. ..

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material is represented by the following chemical formula 1.
An image forming method comprising developing in the presence of a compound represented by: [Chemical 1] (In the formula, A ₁ and A ₂ are divalent aromatic groups and heterocyclic groups,
₁ , G ₂ is a carbonyl group, a sulfonyl group, an oxalyl group,
Phosphoryl group, Z ₁ and Z ₂ are hydrogen atom, hydroxy group,
It represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, or an adsorption accelerating group to silver halide, and L ₁ , L ₂ and R each represent a divalent organic group. )