JPS63265239A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain negative gradient photographic characteristics with very high contrast of <10 gamma by developing a silver halide photographic sensitive material in the presence of a specified compd. CONSTITUTION:A silver halide photographic sensitive material is developed in the presence of a compd. represented by formula I (where Ar is aryl, R1 is H or alkyl, R is alkyl, aryl, alkoxy, aryloxy, acylamino, halogen or alkenyl, m is 1 or 2, n is an integer of 0-3, and in case where n=2 and substituents R are adjacent to each other, the substituents R may form a ring). The content of the compd. in a layer of the sensitive material depends on the characteristics of a silver halide emulsion used, the chemical structure of the compd. and development conditions, so the proper content varies over a wide range. The compd. is useful when added by about 1X10<-6>-1X10<-2>mol. per 1mol. silver in a surface latent image type silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to a method for developing a silver halide photographic light-sensitive material, and in particular provides an extremely high-contrast negative image, a highly sensitive negative image, and a good halftone image quality. It relates to photographic materials.

(8) Prior Art The addition of a hydrazine compound to a silver halide photographic emulsion or developer is known as a developer solution combining ascorbic acid and hydrazine as described in U.S. Pat. No. 3,730,727).
3,227,552N (Using hydrazine as an auxiliary developer to obtain a direct positive color image), 3
, 386.83 ``Specification No. 1 (contains β-monophenyl hydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials), 2.4 'I 9,975 Specification, and ``+ees'' The rheory of Photo
Graphic Pr0CeSSJ No. 0CeSSJ 6th year) 281 pages, etc.

Among these, in particular U.S. Patent No. 2.4 '19,975
No. 1, it is disclosed that high-contrast negative images can be obtained by adding a hydrazine compound.

That is, a hydrazine compound is added to a silver chlorobromide emulsion, and 12
．． It is stated that when developed with a developer having a high pH of 8, extremely high-contrast photographic characteristics with a gamma (r) exceeding 10 can be obtained.

However, a strong alkaline developer having a pH close to 13 is easily oxidized in the air, is unstable, and cannot withstand long-term storage or use. The ultra-high contrast photographic characteristics with a gamma value exceeding 10 are extremely useful for photographic reproduction of continuous-tone images using dot images (dot images) useful in printing plate making, and reproduction of line drawings, whether negative or positive images. Useful.

Conventionally, for this purpose, a silver chlorobromide emulsion with a silver chloride content exceeding 50 mol%, preferably 75 mol% is used, and the effective concentration of sulfite ions is kept extremely low (usually 0.1 mol%). The commonly used method is to develop with a hydroquinone developer (mol/l or less).

However, in this method, due to the low sulfite ion content in the developer, the developer is extremely unstable and cannot be stored for more than 3 days.

Furthermore, since all of these methods require the use of silver chlorobromide emulsions with relatively high silver chloride contents, high sensitivity cannot be obtained.

Therefore, there has been a strong demand for using a highly sensitive emulsion and a stable developer to obtain ultra-high contrast photographic characteristics useful for reproducing halftone images and line drawings.

To this end, U.S. Pat.
No. 4,269.929, No. 4,272,614, No. 4,323.643, etc. disclose silver halide photographic materials that use a stable developer to provide extremely high-contrast negative photographic properties. Although disclosed, the acylhydrazine compounds used therein have been found to have several drawbacks.

That is, these hydrazines are known to generate nitrogen gas during the development process, and this gas may collect in the film to form bubbles, which may damage photographic images.

Therefore, there has been a desire for a compound which can reduce the generation of bubbles and at the same time reduce the cost of producing a sensitive material, and which can provide extremely sharp photographic characteristics even when added in a small amount. Further, if development is continued using these hydrazines, numerous circular fogs (pepper fog) are likely to occur in unexposed areas, which significantly impairs image quality.

In addition, conventional hydrazines are required in large amounts for sensitization and high contrast, and when particularly high sensitivity is required in terms of the performance of the photosensitive material, other sensitization techniques [e.g. chemical Increasing sensitization; increasing particle size: US Patent No. 4
, 272, 606 and 4.241. Adding a compound that promotes sensitization as shown in '164 specification, etc.]
However, when these sensitization techniques are used in combination, sensitization over time during storage and intensification blur may generally occur.

Furthermore, when development is performed using conventional hydrazines,
So-called uneven development is likely to occur due to uneven stirring of the developer. This development unevenness is noticeable in automatic processor processing, and if the development processing is strengthened to eliminate this phenomenon, the above-mentioned sand fog phenomenon occurs, which is a drawback.

Therefore, there has been a desire for a compound that does not have the problems of stability over time, uneven development, or sand fog as described above, is effective when added in a very small amount, and is easy to synthesize.

Previously, the present inventors disclosed oxalate type hydrazines in Japanese Patent Application No. 6'l-20700 and Japanese Patent Application No. 61-22458, but even the compounds based on these inventions are still insufficient. This became clear, and a more effective compound was desired.

(C) Objects of the Invention The first object of the present invention is that it is possible to obtain photographic characteristics of extremely high contrast negative gradation with a gamma of more than 10 using a stable developer. An object of the present invention is to provide a silver halide photographic material.

A second object of the present invention is to provide a negative-working silver halide photographic material containing hydrazines that can provide good image quality without problems with uneven development or sand fog.

A third object of the present invention is to provide a negative-working silver halide photograph containing hydrazines that can provide the desired photographic characteristics of extremely high contrast negative gradation with a small amount of addition without adversely affecting photographic performance. The purpose of the present invention is to provide photosensitive materials.

A fourth object of the present invention is to improve the processing stability (e.g., no development unevenness, sand fog, etc.) by adding hydrazines, which can provide photographic properties such as rapid sharp contrast, to the processing solution. An object of the present invention is to provide a method for developing a silver oxide photographic material with high contrast.

(D) Structure of the Invention The object of the present invention was achieved by developing a silver halide photographic material in the presence of a compound represented by the following general formula (I>).

[In the formula, Ar represents an aryl group, and R1 represents a hydrogen atom or an alkyl group.

R represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a halogen atom, or an alkenyl group.

m represents an integer of 1 or 2, and n represents an integer of 011.2 or 3.

However, when n=2 and the substituents R are adjacent to each other,
The substituents R may form a ring. ] In general formula (I), the aryl group represented by Ar is
Specifically, it is a phenyl group or a naphthyl group that may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an alkenyl group, a substituted Examples include an amino group, an acylamino group, a sulfonamide group, an alkylidene amino group, a thiourea group, a thioamide group, a heterocyclic group, or a combination thereof.

In the general formula (I), the alkyl group among the groups represented by R4 is preferably an alkyl group having 10 or less carbon atoms, such as a halogen atom, a carboxy group, an alkoxy group, an aryloxy group, or a sulfo group. , an aryl group, a substituted amino group, and the like.

In the general formula [I], among the groups represented by R, the alkyl group and alkenyl group are preferably an alkyl group and an alkenyl group having 10 or less carbon atoms, such as a halogen atom, a cyan group, a carboxy group, an alkoxy It may have a substituent such as a group, an aryloxy group, a sulfo group, an aryl group, or a substituted amino group.

-IIQ In formula (I), among the groups represented by R, the aryl group is a phenyl group or a naphthyl group which may have a substituent.

Examples of preferred substituents include alkyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, alkenyl groups, substituted amine groups, and combinations thereof.

In the general formula (I), the alkoxy group among the groups represented by R is preferably an alkoxy group having 1 to 10 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

In the general formula f'I), among the groups represented by R, the aryloxy group is preferably a monocyclic one, and a halogen atom,
It may be substituted with an alkyl group or the like.

Further, Ar or R in the general formula (I) may have a ballast group 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 can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, and the like.

Specific examples of the compound represented by general formula (1) are shown below.

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

(Margin below) (7) (11).

The compound of the present invention can be obtained by the following synthetic scheme:
It can be easily synthesized.

H-R1 (R)n General formula (I[) (R)n(R)n General formula (IV) General formula (V) (R)n General formula (I) [wherein, Ar, R, R1, m and n are defined in the general formula (I), and X represents a halogen atom.

] That is, the amine phenol represented by the general formula (II) and the compound of the general formula (1) having a phenooxalyl group are reacted in an appropriate solvent such as dioxane, benzene, or DMF under a basic catalyst such as triethylamine. to obtain an intermediate of general formula (IV) or general formula (V), and then react with the corresponding hydrazine compound (Ar-NHNH2) to easily obtain the desired compound of general formula CI). be able to.

Hereinafter, the method for synthesizing the compound of the present invention will be explained by giving specific examples.

Synthesis Example 1> Synthesis of Exemplified Compound 1 a) Synthesis of intermediate 4-(phenoxalylamino)phenol To 10.9 g of para-aminophenol was added 200 g of dioxane.
Add triethylamine '1 while stirring at room temperature.
Added 4.7d.

Furthermore, 19.4 g of phenoxalyl chloride was gradually added, and the mixture was stirred at the same temperature for about 1 hour.

After the reaction was completed, the reaction solution was poured into water, the target product was extracted with ethyl acetate, washed with water, and then dried with NaSO4.

After drying the ethyl acetate layer, NazSO+ was removed and the solvent was distilled off under reduced pressure.

The obtained residue was recrystallized from aqueous DMF.

Yield: 23.6g Melting point: 309-310℃ decomposition b)
Synthesis of Exemplified Compound 1 4-(phenoxalylamino)phenol 1 obtained in a)
200 d of ethanol was added to 7.23 g of phenylhydrazine hydrochloride and 2.99 g of phenylhydrazine hydrochloride, and after stirring for a while, 6.98 ml of triethylamine was added and heated under reflux for about 5 hours.

After cooling, the precipitated crystals were collected by filtration and washed with water.

The obtained crude crystals were recrystallized from aqueous dioxane to obtain the desired product.

Yield: 8.759 Melting point: 268.5-270'
C (elemental analysis) 0% H% N% theoretical value
61.98 4.83 15.49 Measured value 61
．． 89 4.93 15.37 Synthesis Example 2> a) Synthesis of intermediate 2,3-dioxo-1,4-benzoxazine 21.1 of orthoaminophenol and 400 d of dioxane
After adding and dissolving, 30.7d of triethylamine
was added, and while stirring at room temperature, phenoxalyl chloride 40.6! 7 was added little by little.

After the addition was completed, the mixture was stirred at the same temperature for about 2 hours, and then the reaction solution was poured into water, and the precipitated crystals were collected by filtration and washed with water and ethyl acetate to obtain the desired intermediate.

Revenue! :15.9y Melting point: 281-282°C decomposition b
) Synthesis of Exemplified Compound 4 150 d of benzene was added to 4.89 g of 2,3-dioxol 1,4-benzoxazine obtained in Synthesis Example 2 a) and 5.84 y of 1-naphthylhydrazine hydrochloride, and while stirring, triethylamine was produced. After the volume was 18ml, the reaction solution was heated under reflux for about 2 hours.

After cooling, the precipitate was collected by filtration and washed with water, and the obtained crystals were recrystallized from aqueous methanol.

Yield: 6.4g Melting point: 247-247.5°C (elemental analysis) 0% H% N% theoretical value 67.
28 4.71 '13.08 Measured value 67.
36 4.80 13.00 Synthesis Example 3> Synthesis of Exemplary Compound 6 Intermediate obtained in a) of Synthesis Example 1, 2.57y of 4-(phenoxalylamino)phenol and 75g of paramethoxyphenylhydrazine hydrochloride To the mixture were added 100 ml of ethanol and 1.4 d of triethylamine, and the mixture was heated under reflux for about 2 hours.

After the reaction, crystals were precipitated when the mixture was allowed to cool.

This was collected by filtration, washed with water, and then recrystallized with ethanol to obtain the desired product.

Yield: '1.9g Melting point: 232-233°C (elemental analysis) 0% H% N% Theoretical value 59.7
9 5.02 13.95 Measured value 59.88
5.16 13.90 In the light-sensitive material of the present invention, the compound represented by the general formula (1) is preferably contained in the surface latent image type silver halide emulsion layer. It may also be contained in a hydrophilic colloid layer adjacent to the layer.

Such layers include a subbing layer, an intermediate layer, a filter layer, a protective layer,
Any layer having any function, such as an antihalation layer, may be used as long as it does not prevent the compound represented by formula (1) from diffusing into the silver halide grains.

The content of the compound of the invention in the layer varies depending on the properties of the silver halide emulsion used, the chemical structure of the compound and the development conditions, so that the appropriate content may vary over a wide range, but the surface latent image A range of about 1.times.10@-6 to 1.times.10@-2 moles per mole of silver in the type silver halide emulsion is practically useful.

When the hydrazine compound represented by the general formula (I) used in the present invention is mixed into the developer,
10” mol/l is suitable, more preferably 5×10
'~5X10-2 mol/f! A range of is particularly preferred.

The silver halide used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide, etc. can be used. However, when silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is preferably in the range of 5 mol % or less.

There are no particular limitations on the morphology, crystal habit, size distribution, etc. of the silver halide grains, but grain sizes of 0.7 microns or less are preferred.

Silver halide emulsions are made of sulfur compounds that form silver sulfide by reacting with gold compounds such as chlorauric acid salts and gold trichloride, silver salts of noble metals such as rhodium and iridium, and stannous salts. Sensitivity can be increased by using reducing substances such as amines without making the particles coarser.

Further, iron compounds such as salts of noble metals such as rhodium and iridium, and blush salts may be present during physical ripening or nucleation of silver halide grains.

In particular, the addition of rhodium salts or complex salts is preferable because it further promotes the effect of the present invention of achieving ultra-high contrast photographic characteristics in a short development time. - In the present invention, the surface latent image type silver halide emulsion refers to an emulsion consisting of silver halide grains having surface sensitivity higher than internal sensitivity, and this emulsion is preferably disclosed in U.S. Pat. No. 4,224,
It has a difference between surface sensitivity and internal sensitivity as specified in the specification of No. 401.

It is desirable that the silver halide emulsion be monodisperse, particularly an emulsion having the monodispersity defined in the above-mentioned US Pat. No. 4,224,401@.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or others.

The 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 include cyanine dyes, merocyanine dyes,
and a pigment belonging to complex merocyanine pigments.

These sensitizing dyes may be used alone or in combination.

Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included 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 sulfate esters Sugar derivatives such as sodium nialginate and starch derivatives: Polyvinyl alcohol , partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bul 1. Soc, Sci, Phot, Jap
Enzyme-treated gelatin such as that described in An.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles,
Mercaptotetrazoles: Mercaptopyrimidines,
Many compounds conventionally known as antifoggants or stabilizers can be added, such as mercaptotriazines, thioketo compounds; azaindenes.

Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazole) and nitroindazoles (eg, 5-nitroindazole).

These compounds may be included in the treatment liquid.

In the photographic light-sensitive material of the present invention, an inorganic or organic hardening agent may be contained in the hydrophilic colloid layer other than the photographic emulsion layer.

For example, chromium salts (chromium 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-8-
triazine, etc.), etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, non-ionic materials such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenylsuccinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Acidic surfactants such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as alkyl carboxylates, alkyl sulfonates, alkyl sulfates, alkyl phosphates anionic surfactants containing groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters; aliphatic or aromatic quaternary@ammonium salts, heterocycles such as pyridinium, imidazolium, etc. Cationic surfactants such as quaternary ammonium salts can be used.

In the photographic light-sensitive material used in the present invention, in the photographic emulsion layer and other hydrophilic colloid layers, for the purpose of improving dimensional stability, etc.
It may contain a decomposed product of a water-insoluble or poorly soluble synthetic polymer.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α
, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and the like can be used.

In order to obtain ultra-high contrast photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use conventional Lith developer or U.S. Pat.
9,975@ It is not necessary to use a highly alkaline developer close to DH13 described in the specification, and a stable developer can be used.

That is, in the silver halide photographic light-sensitive material of the present invention, a developer containing a sufficient amount of sulfite ions as a preservative (particularly 0.15 mol/J or more) can be used, and a developer having a pH of 9,
By using a developing solution with a molecular weight of 5 or more, particularly 10.5 to 12.3, a sufficiently ultra-high contrast negative image can be obtained.

There is no particular restriction on the developing agent that can be used in the method of the present invention, and examples include dihydroxybenzenes, 3-pyrazolidones,
Amine phenols and the like can be used alone or in combination.

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

In addition, if necessary, water softeners, solubilizing agents, toning agents, development accelerators, surfactants, antifoaming agents, hardeners, and film silver stain preventive agents (for example, 2-mercaptobenzimidazole sulfonic acid) It may also include.

Specific examples of these additives are described in Research Disclosure No. 176, No. 17643, and the like.

As the fixer, one having a commonly used composition can be used.

As a fixing agent, in addition to thiosulfate and thiocyanate,
Organic sulfur compounds known to be effective as fixing agents 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 method may be adopted in which a developing agent is incorporated into the photosensitive material and the material is processed with an alkaline activator solution.

(Unexamined Japanese Patent Publication No. 57-129436, No. 57-129433
No. 57-129434, No. 57-129435, U.S. Patent No. 4.323.643, etc.).

The treatment temperature is usually selected between 18°C and 50°C, but 1
The temperature may be lower than 8°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 when the photosensitive material is placed in an automatic processor to when it comes out is set to 60 seconds to 120 seconds, sufficient photographic characteristics with ultra-high contrast and negative gradation can be obtained.

(E) Example <Example 1> Average particle size 0.97% containing A (78r, 3% AgI).
A silver iodobromide emulsion consisting of 25 μm cubic crystals was prepared by a double jet method, washed with water in a conventional manner, redissolved, and then chemically sensitized using sodium thiosulfate.

After dividing this silver iodobromide emulsion into nine parts, the compounds (2), (6), (7) of the general formula (I) of the present invention and the comparative compound (, A) were added in the amounts shown in Table 1. After that, it was coated on a polyester film so that the amount of silver was 3.7 g per film.

After wet exposure was applied to the film sample prepared in this way, a developer having the composition shown below was used for 20'
Developing was performed at C for 1 to 5 minutes.

Developer solution> Hydroquinone 30 g4-
Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.3 g Sodium sulfite 75 g EDTA・2
Na 1.0g Tripotassium phosphate 80g Potassium bromide
2.0g NaO813g 5-methylbenzotriazole 0.391-diethylamino-2,3-dihydroxypropane 17g Add water and adjust to pH 11.5 with 11 potassium hydroxide.

(Margin below) Comparative compound (A> The results are shown in Table ■.

As is clear from the artificial, the compound of the present invention is different from the comparative compound (
Compared to A), it can be seen that the high-contrast photographic properties were achieved even after 1 minute of development at 20° C., and there was no increase in fog even after long-term development.

Furthermore, the sensitivity change due to the change in development time is different from that of the comparative compound (A>
It can be seen that the stability against development is high because it is extremely small compared to .

In addition, when looking at the unexposed areas of each sample after the development process, it was found that in the sample (Nα 2.3) to which the comparative compound (A> was added), obvious sand fog had already occurred after 3 minutes of development time. The sample containing the compound of the present invention (~α
4 to 9), no sand fog was observed.

<Example 2> Next, another part of the film sample obtained in Example 1 was used to test the quality of halftone dots.

That is, using a 150 line gray contact screen,
After each film sample was exposed to light through the Sensimetry Kagiri Kotsutsuji, it was incubated at 38°C with the same developer as before.
The image was developed for 0 seconds and the quality of halftone dots was checked.

The results are shown in Table ■.

The halftone dot quality is visually evaluated on a five-level scale, with 5 representing the best quality and 1 representing the worst quality. As halftone dot original plates for plate making, grades 5 and 4 are practically usable, grades 3 are poor but barely usable, and grades 2 and 1 are of a quality that is practically unusable.

(The following is a blank space) Table ■> As is clear from Table ■, it can be seen that the compounds of the present invention exhibit good halftone dot quality.

<Example 3> After wet exposure was applied to another part of the film No. 1 sample (no high contrast agent added) obtained in Example 1, the developer of the present invention was applied to the developer described in Example 1. Compounds (5), (6
), (12) with 1 developer solution each! 1.5 mmo per
le was added.

Furthermore, as a comparison, comparative compounds (B) and (C) were also added at 1.5 mmol per developer solution 11 at 20'C.
The film was developed for 2.4.6 minutes, and photographic properties were determined.

Comparative compound (B) Comparative compound (C) The results are shown in Table ■.

As is clear from Table 3, the compound of the present invention has a faster start-up of development than the comparative compound (B), and has high contrast photographic characteristics even after a 20'C2 minute development process.
Moreover, it can be seen that there is no increase in fog even after long-term development.

Furthermore, these things are true for compounds (5), (6), and
This becomes even clearer by comparing (12) with comparative compound (C).

(Margin below)

Claims (1)

[Scope of Claims] 1) An image forming method characterized by developing a silver halide photographic light-sensitive material in the presence of a compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group, and R_1 represents a hydrogen atom or an alkyl group. group, acylamino group, halogen atom, or alkenyl group. m represents an integer of 1 or 2, and n represents an integer of 0, 1, 2, or 3. However, when n = 2 and the substituents R are adjacent to each other for,
The substituents R may form a ring. )