JPS62178246A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain photographic characteristics of a hard contrast negative gradation exceeding 10 gamma and good image quality having no uneven development and sand fogging by developing a silver halide photographic sensitive material in the presence of a specific compd. CONSTITUTION:The silver halide photographic sensitive material is developed in the presence of the compd. expressed by the formula I, where Ar is an aryl group, R is a hydrogen atom, alkyl group, alkenyl group, unsatd. heterocyclic group, aryl group, R1, R2 are a hydrogen atom or the group expressed by the formula II; R0 is an alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, n is 1 or 2 integer. The compd. is preferably incorporated into the surface latent image type silver halide emulsion layer and the content thereof is about 1X10<-6>-1X10<-2>mol per mol of silver. The hydrazine compd. expressed by the formula I is adequately incorporated at 10<-4>-10<-1>mol/l in the case of incorporating said compd. into a developing soln.

Description

Detailed Description of the Invention (^) Industrial Application Field The present invention relates to a method for developing silver halide photographic materials, and particularly provides extremely high-contrast negative images, highly sensitive negative images, and good halftone image quality. It relates to photographic materials.

(8) Prior Art Adding a hydrazine compound to a silver halide photographic emulsion or a ring imager is described in U.S. Pat.
No. 3,227,552 (using hydrazine as an auxiliary developer to obtain a direct positive color image), No. 3
, 386,831 (contains β-monophenyl hydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials), 2.419.975@ specification, and MeeS
Author [The Theory of Photography]
ic Process J 3rd edition (1966) page 281.

Among these, US Pat. No. 2,419,975 in particular discloses that a high-contrast negative image 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 88, extremely high-contrast photographic characteristics with a gamma (γ) of over 10 can be obtained.

However, a strong alkaline developer with an II 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 useful for photographic reproduction of continuous-tone images using halftone images (dot ima (le)) or reproduction of line drawings, which are useful for printing plate making, whether negative or positive images. It is extremely 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 containing mol/β 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. 269.929, No. 4,272,614, No. 4,
No. 323.643 and other publications disclose silver halide photographic materials that use a stable developer to provide extremely high-contrast negative photographic properties, but the acylhydrazine compounds used therein have several drawbacks. It has been found that there is.

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

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. Also, if development is continued using these hydrazines, countless circular fogs (sand fogs) will appear in the unexposed areas.
pepper' fO(1) was likely to occur, significantly impairing 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
However, when these sensitization techniques are used together,
Generally, sensitization and enhancement blurring may occur over time during storage.

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 self-developing processing, and when the development processing is strengthened to eliminate this phenomenon, the above-mentioned sand fogging 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.

(C) Purpose of the Invention The purpose of the present invention is, firstly, to develop a gamma film using a stable developer.
The object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining photographic characteristics of extremely high contrast negative gradation with a value exceeding 10.

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).

General formula (I> A r-N-N-C-C-0-R 1R2 [wherein, Ar represents an aryl group, R is a hydrogen atom, an alkyl group, an alkenyl group, an unsaturated heterocyclic group, or Represents an aryl group.

R1 and R2 represent a hydrogen atom or a group represented by general formula (n). ] General formula (II>+C'R (wherein, Ro represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and n is 1
or represents an integer of 2. [In the general formula (I>), the aryl group represented by Ar is specifically an engineering group or a naphthyl group, which may have a substituent, and examples of the substituent include: Alkyl group, aryl group, halogen atom, alkoxy group, aryloxy group, alkenyl group, substituted amino group, acylamino group, sulfonamide group, alkylidene amino group, thiourea group, thioamide group, heterocyclic group, or combinations thereof, etc. can be mentioned.

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 30 or less carbon atoms, including a halogen atom, a cyano group, and a carboxy group. , an alkoxy group (including a polyether group), an aryloxy group, a sulfo group, an aryl group, a substituted amine group, and the like.

In the general formula (1), 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 substitutions include alkyl groups, aryl groups,
Examples include halogen atoms, alkoxy groups, aryloxy groups, alkenyl groups, substituted amino groups, acylamino groups, sulfonamide groups, alkylidene amino groups, heterocyclic groups, and combinations thereof.

Among the groups represented by R in the general formula (I>), an unsaturated heterocyclic group may be combined with a monocyclic or bicyclic aryl group to form a heteroaryl group.

In the general formula (II>), among the groups represented by Ro, the alkyl group and alkenyl group are preferably an alkyl group and an alkenyl group having 30 or less carbon atoms, and a halogen atom,
It may have a substituent such as a cyan group, an alkoxy group, an aryloxy group, an aryl group, or a substituted amine group.

In the general formula (II), among the groups represented by Ro, the aryl group is a phenyl group or a naphthyl group which may have a substituent, and examples of the substituent are an alkyl group, an aryl group, and a naphthyl group. group, a halogen atom, an alkoxy group, an aryloxy group, or a combination thereof.

Among the groups represented by Ro in the general formula (II>), the alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom or an aryl group.

In the general formula (II), the aryloxy group in the group represented by Ro is preferably a monocyclic one, and a halogen atom,
It may be substituted with an alkyl group or the like.

Ar or R in 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 (I) are shown below.

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

(Margin below) 16° The compounds of the present invention can be synthesized by various methods.

For example, it can be easily obtained by reacting the corresponding hydrazine compound (ArNHNH2) with a compound represented by the general formula (In> in a suitable solvent such as dioxane, benzene, DMF, etc. under a base catalyst or simply by heating.

General formula (III> SoR-0-C-C-XC In the formula, R is defined in the general formula (I),
X represents a halogen atom, a phenoxy group, a succinimide group, a phthalimide group, or the like. ] As a further alternative,
As shown in the synthesis example, a method using a transesterification reaction, a method of reacting ascorbic acid with a corresponding diazonium salt, etc. can be used.

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

Synthesis Example 1> Synthesis of Exemplified Compound 1 150 d of diethyl oxalate was added to 30.7 g of p-nitrophenylhydrazine, and the mixture was heated in a water bath at about 80'C for 1 hour.
The mixture was heated and stirred for hours. After cooling, 50 d of isopropyl ether was added to the reaction solution to precipitate crystals.

Recrystallization was performed using the obtained crude crystals and an ethyl acetate-benzene mixture to obtain 40.69 of 1-ethoxalyl-2-(p-nitrophenyl)hydrazine.

Melting point: 187.0-187.5°C Next, the 1-ethoxalyl-2-(1)-nitrophenyl)hydrazine obtained above at 25.3°C was mixed with ethanol at 300 d.
, after dissolving in a mixed solvent of dioxane 200me, 1
20 g of 0% palladium-carbon was added and catalytic reduction was carried out in a conventional manner to obtain 21.5 g of 1-ethoxalyl-2-(p-aminophenyl)hydrazine. Melting point: 97-99°C Next, 11.29 of 1-ethoxalyl-2-(p-aminophenyl)hydrazine obtained above was dissolved in 200 d of ethanol, and 10.99 of p-n-hexyloxybenzaldehyde was added. and stirred at room temperature overnight.

After the reaction, the precipitated crystals were collected by filtration and recrystallized with about 11 ml of ethanol to obtain Exemplified Compound 1.

Yield: 19.89 Melting point: 206. O~207.0
°C (elemental analysis) 0% 11% N% Theoretical value: 67.13 7.10 10.21 Measured value: 67.10 7.08 10.35 Synthesis Example 2> Synthesis of Exemplary Compound 4 Diethyl oxalate 13ml, 1.4 ml of triethylamine was added to 10 d of cyclohexane, and 1.75 g of p-methoxyphenylhydrazine hydrochloride was added little by little while stirring at room temperature.

After the addition, the mixture was heated under reflux for 1 hour.

After cold welding, the precipitated crystals were collected by filtration, washed with water and dried.

The obtained crude crystals were recrystallized from a mixed solvent of ethyl acetate and cyclohexane to obtain Exemplary Compound 4.

Yield: 1.69 Melting point: 130. O~131.
5°C (elemental analysis) 0% H% N% Theoretical value: 55.46 5.92 11.76 Measured value: 55.4'l 5.93 11.68 Synthesis Example 3> Synthesis of Exemplified Compound 6 L- A solution of 8.459 ascorbic acid dissolved in 85 ml of water and 4-methylbenzenediazonium sulfate dissolved in 120 ml of water
The solution dissolved in m was mixed and stirred at room temperature for 1 hour. After cooling the reaction solution with water, the precipitate was collected by filtration, washed with cold water, and dried to obtain pale yellow crystals.

Yield: 11.3g Melting point: 180.5-182.5℃
(Elemental analysis) 0% H% N% theoretical value:
53,06 4.80 9.52 Measured value:
53.00 4.96 9.65 Synthesis Example 4> Synthesis of Exemplary Compound 7 A solution of 9.23 g of L-ascorbic acid dissolved in 90 ml of water and 4-methoxybenzenediazonium sulfate were added to 1 ml of water.
The solution dissolved in 10d was mixed and stirred at room temperature for 1 hour. After cooling the reaction solution with water, the precipitate was collected by filtration, washed with cold water, and then dried to obtain Exemplary Compound 7 as pale yellow crystals.

Yield: 10y Melting point: 175.5-177°C
(Elemental analysis) 0% 1”% N% Theoretical value:
50.32 4,55 9.03 Measured value:
50.30 4,36 9.16 Synthesis Example 5>
Synthesis of Exemplified Compound 8 A solution obtained by dissolving 1.55 g of Exemplified Compound 7 obtained in Synthesis Example 4 in 20 m of dioxane and a solution obtained by dissolving 0.13 g of sodium metal in 5 ml of anhydrous n-octyl alcohol were mixed. The mixture was heated and stirred on a 90°C water bath for 4 hours.

After cooling and removing insoluble matter by filtration, the filtrate was concentrated under reduced pressure, and the resulting residual aroma was recrystallized from a mixed solvent of cyclohexane and ethyl acetate to obtain Exemplary Compound 8.

Yield: 0.9i Melting point: 89.5-92.5°
C (elemental analysis) 0% H% N% theoretical value:
63.33 8.13 8.69 Measured value:
63.32 8.20 8.73 Synthesis Example 6> Synthesis of Exemplary Compound 10 2.38tj of p-tolylhydrazine hydrochloride was added with TI-(F
After adding 30m, add 2.43 force, dry ice -
While cooling in a methanol bath, a solution of 3.31 g of octylchloroglyoxilade dissolved in 15yf of THF was slowly added dropwise. After the dropwise addition, the mixture was stirred at the same temperature for 3 hours, the precipitate was filtered off, the filtrate was concentrated under reduced pressure, and silica gel column chromatography was performed to obtain the target exemplary compound 10.

1[ii: 2.8g Melting point: 114.0-1
15.0'C (elemental analysis) 0% H% N
% theoretical value: 66.64 8.55 9.1
4 Measured values: 66.64 8.60 9.1
3 Synthesis Example 7> Synthesis of Exemplified Compound 11 4-(4-tert-butylphenoxy)-phenylhydrazine hydrochloride 2.929 and diethyl oxy 4-nolate 1
After adding 10 ml of cyclohexane and 1.39 ml of triethylamine to 4.61 g, the mixture was heated under reflux for 3 hours.

Upon completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, dried over boric acid, and ethyl acetate was poured out under reduced pressure.

Exemplary compound 11 was obtained by recrystallizing the obtained residual aroma from a mixed solvent of cyclohexane and ethyl acetate.

Yield: 2.6y Melting point: 117. O~118.
0'C (elemental analysis) 0% H% N% Theoretical value: 67.40 6.79 7.86 Measured value: 67.31 6.80 7.93 In the photosensitive material of the present invention, general formula (1) The compound represented by
It is preferably contained in the surface latent image type silver halide emulsion layer, but it may be contained in the hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer.

Such layers include a subbing layer, an intermediate layer, a filter layer, a protective layer,
The layer may have any function, such as an antihalation layer, as long as it does not prevent the compound represented by formula (I) 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@-' to 1.times.10@-2 moles per mole of silver in the type silver halide emulsion is practically useful.

When mixed in the developer with the hydrazine compound represented by the general formula (1) used in the present invention, 104 to
10-1 mol/l is suitable, more preferably 5X1
The range of C)' to 5X10-2# 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 gold compounds such as chlorauric acid salts and gold trichloride, salts of noble metals such as rhodium and iridium, sulfur compounds that react with silver salts to form silver sulfide, stannous salts, etc. Sensitivity can be increased by using reducing substances such as amines without making the particles coarser.

Further, salts of noble metals such as rhodium and iridium, and iron compounds such as red blood 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, a surface latent image type silver halide emulsion refers to an emulsion comprising silver halide grains having surface sensitivity higher than internal sensitivity, and this emulsion is preferably described in US 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, soudyryl 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 hypersensitization.

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,
The emulsion may contain a substance exhibiting hypersensitization.

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 alginate 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-treated gelatin, acid-treated gelatin, Bull, Soc, Sci, Phot, and Japa.
Enzyme-treated gelatin as described in Na16, P2O (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

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 benzodeazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles. ; mercaptopyrimidines, mercap-1-triazines, thioketo compounds; azaindenes; and many other compounds conventionally known as antifoggants or stabilizers can be added.

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

These compounds may be included 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 and other hydrophilic colloid layers.

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 contained for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactant; alkyl carboxylate,
Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as alkyl sulfonates, alkyl sulfates, and alkyl phosphate esters; amino acids , aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters; cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium; Agents 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, hydroxyalkylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. can be used as a monomer component.

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 having a pH close to 13 as described in the specification, and a stable developer can be used.

That is, the silver halide photographic light-sensitive material of the present invention can use a developer containing a sufficient amount of sulfite ions as a preservative (particularly 0.15 mol/2 or more), and has a pH of 9.
. , 5 or higher, particularly 10.5 to 12.3, it is possible to obtain sufficiently ultra-high contrast negative images.

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 acids) It may also include.

Specific examples of these additives are described in Research Disclosure 1F No. 6 No. 17643.

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. Pat. 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 0.2 containing 97% AO8r and 3% Ag■
A silver iodobromide emulsion consisting of 5μ cubic crystals was prepared by the double jet method, washed with water and redissolved by the usual method, and then
Chemical sensitization was performed using sodium thiosulfate.

After dividing this silver iodobromide emulsion into 17 parts, compounds (1), (8), (10) (11) of the general formula (I> of the present invention)
, (12), (13), (20) and comparative compound (A)
were added in the amounts shown in Table 1, and then coated on a polyester film in an amount of 3.7 g of silver per Tri.

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

Developer solution> Hydroquinone 30 g4-
Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.37 Sodium sulfite 75 gEDTA・2
Na 1.09 Tripotassium phosphate 80 g Potassium bromide
2.0g NaO813g 5-methylbenztriazole 0.391-diethylamine-2,3-dihydroxypropane 17 Add 7 water and adjust to pH 11.5 with 1 fl potassium hydroxide.

Comparative compound (A) The results are shown in Table 1.

As is clear from Table 1, the compound of the present invention is different from the comparative compound (
It can be seen that compared to A>, the high-contrast photographic characteristics were better achieved even after 20'C1 minute of development, and there was no increase in fog even after long-term development.

Furthermore, the sensitivity change due to the change in development time was higher than 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 (Nα
4 to 17), no sand fog was observed.

<Example 2> Next, a part of the film sample obtained by 1q in Example 1 was
After heating at C for 30 days, exposure and development (20°C for 3 minutes) were performed in the same manner as in Example 1, and the sensitivity and fog values immediately after coating were compared. The results are shown in Table ■.

(The following is a blank space) As is clear from Table 3, it can be seen that the compounds of the present invention exhibit extremely little change in sensitivity and increase in fog over time of storage.

<Example 3> Next, using another part of the film sample obtained in Example 1, a halftone quality test was conducted.

That is, using a 150 line gray contact screen,
After exposing each film sample to light via a sensimetry light wedge, it was incubated at 38°C with the same imaging solution as before.
Developed for 2 seconds and checked the dot quality.

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, 5 and 4 are practically usable, 3 is poor quality but barely usable, and 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.

Claims (1)

[Claims] (1) A silver halide photographic light-sensitive material is expressed by the following general formula (I):
An image forming method characterized by developing in the presence of a compound represented by: General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Ar represents an aryl group, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an unsaturated heterocyclic group, or an aryl group. R_1 and R_2 represent a hydrogen atom or a group represented by general formula (II). ] General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_0 represents an alkyl group, alkenyl group, aryl group, alkoxy group, or aryloxy group, and n represents an integer of 1 or 2. ]