JPH05289226A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material capable of forming an image extremely high in contrast, small in occurrence of grained fog with high sensitivity by rapid development processing using a stable developing solution high in sulfite concentration and capable of forming an image improved in rise of sensitivity and restrained in increase of grained fog by using even a developing solution raised in activity due to fatigue, etc., with the lapse of time or the like. CONSTITUTION:The silver halide photographic sensitive material contains at least one of hydrazine compounds represented by formula 1 and at least one of tetrazaindene compounds represented by formula II, and in formulae I and II, Ar is aryl; R is -OR1 or -N(R2) (R3); each of R4-R6 is H, an alkyl, alkenyl, or an alkylthio; each of R4 and R5 may form a 5- or 6-membered ring together with each other and they have >=3C; and R7 is hydroxy or mercapto.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material used in a photoengraving process and capable of stably forming a negative image of high sensitivity and ultra-high contrast. It is about.

[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 extremely useful for photographic reproduction of continuous tone images by dot image useful for printing plate making or reproduction of line drawings regardless of whether it is a negative image or a positive image. It is useful.

For such a purpose, conventionally, a silver chlorobromide emulsion having a silver chloride content of more than 50 mol%, preferably more than 75 mol% was used, and the effective concentration of sulfite ion was extremely low (usually). A method of developing with a hydroquinone developer (0.1 mol / l or less) was generally used (lith development).

However, according to this method, since the sulfite ion in the developer is low, the developer 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
4 and 4,323,643, etc., a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added is used, and a sulfite preservative is added at a pH of 11.0 to 12.3. A system has been proposed which forms a very hard negative image by processing with a developer containing 15 mol / l or more and having good storage stability. This new image forming system is characterized in that it is possible to use silver iodobromide or silver chloroiodobromide, whereas only conventional silver chlorobromide having a high silver chloride content can be used in lith development.

However, the acylhydrazine compounds used therein are known to generate nitrogen gas during the development process, and this gas may collect in the film to form bubbles, which may impair the photographic image.

Therefore, for the purpose of reducing the generation of air bubbles and at the same time, reducing the cost of producing a light-sensitive material, a sufficient maximum density can be obtained with a high contrast even with a small amount of addition, and uneven development and sand fog can be prevented. A silver halide photographic light-sensitive material containing a hydrazine compound which is difficult to generate is disclosed in JP-A-62-17882.
46, Dosho 62-180361, Dosho 62-27524
7 and 63-253357.

However, when this light-sensitive material is treated with a developer whose activity has increased due to fatigue over time, nucleating and developing with a hydrazine compound is promoted, resulting in increased sensitivity, sudden thickening of halftone dots, innumerable sand fog, etc. Was found to occur. This phenomenon occurs regardless of which hydrazine is used, and therefore a countermeasure has been required. At the same time as the remarkable high-sensitivity contrast, countless circular fog (sand fog) is easily generated due to the infectious development in the unexposed area, and the image quality is significantly impaired, which is a serious problem in the photolithography process.

[0012]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining extremely high contrast and high-sensitivity photographic characteristics by using a stable developing solution. Is to provide.

Secondly, an object of the present invention is to provide a silver halide photographic light-sensitive material exhibiting super-high contrast photographic characteristics and having less generation of sand fog.

Thirdly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is less susceptible to increase in sensitivity and less in sand fog even when treated with a developer having increased activity due to fatigue over time.

[0015]

It is an object of the present invention to have at least one light-sensitive silver halide emulsion layer on a support, the silver halide emulsion layer or another hydrophilic colloid layer having the following structure. A silver halide photographic light-sensitive material containing a compound represented by Chemical formula 3 wherein the silver halide emulsion layer contains at least one compound represented by Chemical formula 4 below. Achieved with a photographic light-sensitive material.

[0016]

[Chemical 3]

[Wherein Ar represents an aryl group, and R
Is a group represented by -OR ₁ or -N (R ₂ ) (R
₃ ) represents a group represented by. R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted unsaturated heterocyclic group, or a substituted or unsubstituted aryl group. R ₂ , R ₃
Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted unsaturated heterocyclic group, or a substituted or unsubstituted pyridinium group. R ₂ and R ₃ may be linked to each other to form a ring. ]

[0018]

[Chemical 4]

[In the formula 4, R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or an alkylthio group. , R ₄ and R ₅ may together form a 5- or 6-membered ring. However, the total number of carbon atoms of R ₄ and R ₅ is 3 or more. R ₇ represents a hydroxy group or a mercapto group. ]

In the chemical formula 3, the aryl group represented by Ar is specifically a phenyl group which may have a substituent, or a naphthyl group, and examples of the substituent include an alkyl group, Aryl group, hydroxyl group, halogen atom, alkoxy group, aryloxy group, alkenyl group, amino group, acylamino group, sulfonamide group, alkylideneamino group, ureido group, thiourea group, thioamide group, heterocyclic group, or a combination thereof. Etc.

Further, Ar may have a ballast group incorporated therein, which is commonly used in non-moving photographic additives such as color couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inactive for photographic properties, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group and a phenoxy group.

In Chemical formula 3, R represents a group represented by —OR ₁ or a chemical group represented by Chemical formula 5.

[0023]

[Chemical 5]

R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted unsaturated heterocyclic group, or a substituted or unsubstituted aryl group.

R ₂ and R ₃ are each independently a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted unsaturated heterocyclic group, or a pyridinium group represented by Chemical formula 6. R ₂ and R ₃ may be linked to each other to form a ring.

[0026]

[Chemical 6]

R ₈ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group. R ₉ is a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. X ⁻ represents an anion.

Next, specific examples of the compound represented by the formula 3 of the present invention will be given, but the scope of the present invention is not limited to these.

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

[0049]

[Chemical 27]

[0050]

[Chemical 28]

[0051]

[Chemical 29]

[0052]

[Chemical 30]

[0053]

[Chemical 31]

[0054]

[Chemical 32]

[0055]

[Chemical 33]

[0056]

[Chemical 34]

[0057]

[Chemical 35]

[0058]

[Chemical 36]

[0059]

[Chemical 37]

[0060]

[Chemical 38]

[0061]

[Chemical Formula 39]

[0062]

[Chemical 40]

[0063]

[Chemical 41]

[0064]

[Chemical 42]

[0065]

[Chemical 43]

[0066]

[Chemical 44]

[0067]

[Chemical 45]

[0068]

[Chemical 46]

[0069]

[Chemical 47]

[0070]

[Chemical 48]

[0071]

[Chemical 49]

[0072]

[Chemical 50]

[0073]

[Chemical 51]

[0074]

[Chemical 52]

[0075]

[Chemical 53]

[0076]

[Chemical 54]

[0077]

[Chemical 55]

[0078]

[Chemical 56]

[0079]

[Chemical 57]

[0080]

[Chemical 58]

[0081]

[Chemical 59]

[0082]

[Chemical 60]

[0083]

[Chemical formula 61]

[0084]

[Chemical formula 62]

[0085]

[Chemical 63]

[0086]

[Chemical 64]

[0087]

[Chemical 65]

[0088]

[Chemical 66]

[0089]

[Chemical 67]

[0090]

[Chemical 68]

[0091]

[Chemical 69]

[0092]

[Chemical 70]

[0093]

[Chemical 71]

[0094]

[Chemical 72]

[0095]

[Chemical formula 73]

[0096]

[Chemical 74]

[0097]

[Chemical 75]

[0098]

[Chemical 76]

[0099]

[Chemical 77]

[0100]

[Chemical 78]

[0101]

[Chemical 79]

[0102]

[Chemical 80]

[0103]

[Chemical 81]

[0104]

[Chemical formula 82]

[0105]

[Chemical 83]

[0106]

[Chemical 84]

[0107]

[Chemical 85]

[0108]

[Chemical formula 86]

[0109]

[Chemical 87]

[0110]

[Chemical 88]

The compound represented by Chemical formula 3 in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers.
Since the content of the compound of formula 3 of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can be varied over a wide range. A range of about 10 ^{−6 to} 5 × 10 ⁻² mol per mol of silver in the silver halide emulsion is practically useful, and a range of 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable.

Addition of a tetrazaindene compound to a silver halide photographic emulsion is a technique known to those skilled in the art as described in "Photochemistry" (Photo Kogyo Publishing Co., Ltd.), Further, a technique for adding a hydroxytetrazaindene compound to a silver halide photographic emulsion containing a hydrazine compound is disclosed in JP-A-53-84714 and JP-A-6-74714.
4-65541.

However, with the hydrazine compounds disclosed in these publications, when processed with a developer having increased activity due to fatigue over time, sensitivity increases and sand fog increases, which is due to the disclosed tetrazaindene compounds. I can't control it.

Even the hydrazine compound represented by the formula 3 of the present invention, 4-hydroxy-6-methyl-1,3,3a, 7, which has been conventionally added to a photosensitive emulsion in the photographic industry, is used.
-In the case of tetrazaindene, the effect of the present invention is hardly seen. That is, it was found that the problem of the fatigue developing solution can be overcome only by the combination of the compound of Chemical formula 3 and the compound of Chemical formula 4 of the present invention.

Specific examples of the compound represented by Chemical formula 4 will be given below, but the scope of the present invention is not limited thereto.

[0116]

[Chemical 89]

[0117]

[Chemical 90]

[0118]

[Chemical Formula 91]

[0119]

[Chemical Formula 92]

[0120]

[Chemical formula 93]

[0121]

[Chemical 94]

[0122]

[Chemical 95]

[0123]

[Chemical 96]

[0124]

[Chemical 97]

The compound represented by Chemical formula 4 in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers.
Since the content of the compound of formula 4 of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the developing conditions, the appropriate content can be varied over a wide range. A range of about 5 × 10 ^{−6 to} 5 × 10 ⁻² mol is practically useful, and more preferably a range of 1 × 10 _{−4 to} 3 × 10 ⁻² mol per mol of silver in the silver halide emulsion. Is good.

The silver halide emulsion used in the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. Alternatively, when 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 used in the present invention are not particularly limited, but those having an average grain size of 0.7 micron or less, particularly 0.5 micron or less are preferable. It is preferable that 90% or more of all particles have a particle diameter within the range of ± 10% of the average particle diameter. The preparation method of silver halide emulsion is forward mixing, reverse mixing,
Any known method such as simultaneous mixing may be used.

The emulsion that had been physically ripened was desalted and then
Although it is preferable to apply the necessary additives, the desalting treatment can be omitted.

The silver halide emulsion used in the present invention is
Chemical sensitization can be performed by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allyl isothiocyanate, cystine, and rhodanine, U.S. Pat. Nos. 1,574,944, 2,278,947, 2,410,689, Sulfur-containing compounds as described in No. 2,440,206, No. 3,187,458, No. 3,415,649, No. 3,501,313 and the like can be used. In addition to sulfur sensitization, US Patent Nos. 2,448,060 and 2,540,086
No. 2,556,245 and No. 2,566,263, the sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium and ruthenium can be used in combination. Further, a sensitizing method using various gold compounds such as potassium chloroaurate and auric trichloride and palladium compounds such as palladium chloride can be used in combination.

In the light-sensitive material of the present invention, in addition to the light-sensitive emulsion layer, an overcoat layer, an intermediate layer, a backcoat layer, an undercoat layer and other hydrophilic colloid layers can be provided. A matting agent may be contained in those layers.

As the binder or protective colloid that can be used in the emulsion layer, overcoat layer, intermediate layer, backcoat layer and the like of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic substances are used. A sex colloid 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, Various synthetic hydrophilic polymer substances such as partial acetals of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide and polyvinyl imidazole can be used, such as single or copolymers. As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or oxygen-processed gelatin as described in Bull.Soc.Sci.Phot.Japan, No.16, P30 (1966) may be used, or gelatin. A hydrolyzate or an oxygen hydrolyzate can also be used.

The photographic emulsion used in the present invention includes known stabilizers such as mercaptotetrazole, mercaptotriazole, benzotriazole and benzimidazole, antifoggants, polyalkylene oxides, thioether compounds, quaternary ammonium salt compounds and the like. Various development accelerators can be contained.

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 (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.

Further, in a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (eg, , Development acceleration, contrast enhancement, and sensitization) may be included for various purposes. 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; anionic surfactants containing acidic groups such as carboxyl groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups such as alkylcarboxylic acid salts, alkyl sulfuric acid esters, and alkyl phosphoric acid esters Agents; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium What cationic surfactant 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 and other hydrophilic colloid layers 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.

Any support known in the art can be used in the photographic light-sensitive material used in the present invention. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (for example, polyethylene, polypropylene, etc.) laminated paper, polystyrene film, polycarbonate film, and metal plate such as aluminum. These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to undercoating treatment by a known method.

In order 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 is not particularly limited, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. In addition to the above, the developer contains a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, bromide, iodide, and organic antifoggant (particularly preferably,
Development inhibitors or antifoggants such as nitroindazoles or 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 described in Research Disclosure 176, No. 1
7643 and the like.

In the present invention, a system in which a developing agent is incorporated in a light-sensitive material and processing is carried out with an alkaline activator solution may be adopted. (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.

[0139]

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

Example 1 A cubic monodisperse silver iodobromide emulsion having an average particle size of 0.25 micron was prepared by the pAg controlled double jet method, and desalted, washed with water and redissolved by the flocculation method. The silver iodide content was set to 1.5 mol% so that the silver iodide was distributed evenly throughout the grain.

This emulsion was sensitized with sulfur by a conventional method and then 1
-Phenyl-5-mercaptotetrazole was added, and the tetrazaindene compound of formula 91 of the present invention was added to each of them in an amount of 5 × 10 _-4 mol / mol Ag.
The hydrazine compounds of the present invention and the comparative examples shown in Table 1 were mixed with 5 ×
10 ⁻⁴ mol / mol Ag was added, and further 2-hydroxy-
After adding 4,6-dichloro-1,3,5-triazine sodium salt and sodium dodecylbenzene sulfonate, silver nitrate was coated on the polyethylene terephthalate film at 5 g / m @ 2 and gelatin at 3 g / m @ 2. As a protective layer, 1 g of gelatin, and a surfactant, a matting agent and a hardener were added and coated thereon to prepare 7 kinds of samples shown in Table 1. The hydrazines of the comparative examples tested are shown below.

[0142]

[Chemical 98]

[0143]

[Chemical 99]

Each sample thus obtained was exposed and developed to measure its sensitivity value. A tungsten lamp was used for the exposure, and the sensitivity value was determined as the exposure amount required to obtain a transmission density of 3.0. Table 1 shows the relative value when the sensitivity value of the sample containing no hydrazine compound is 100. It showed with. Further, gamma is represented by tan θ in the linear portion where the optical density is 1.0 to 2.5. Develop with the developer of the following composition
It was developed at 30 ° C. for 30 seconds, fixed, washed with water and dried.

Further, as a test for sand fog, each sample was forcibly developed with the same developer at 38 ° C. for 60 seconds, and the occurrence thereof was examined. The results are shown in Table 1. The sand fog was visually evaluated on a scale of 5, with 5 being the best and 1 being the worst. 5 and 4 are practical, 3 is poor, but practically practical, and 2 and 1 are not practical.

Further, in order to test the characteristics when treated with a developer having increased activity due to fatigue over time, after leaving the following developer in an open container for one week, each photosensitive material was exposed and developed in the same manner as above. Processed. The test and evaluation of sand fog were conducted in the same manner as above.

<Developer> Hydroquinone 50.0 g N-methyl-p-aminophenol 1 / 2H ₂ SO ₄ 0.3 g Sodium hydroxide 18.0 g 5-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g EDTA · 2Na 1 0.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzene imidazole-5-sulfonic acid 0.2 g 3- (5-Mercaptotetrazole) benzene sodium sulfonate 0.2 g Sodium toluenesulfonate 8. Add 0 g water and adjust to pH 11.8 with 1 l potassium hydroxide.

[0148]

[Table 1]

From the results shown in Table 1, the photographic light-sensitive material of the present invention gave a harder image than the photographic light-sensitive material of Comparative Example.
With a developer having less generation of sand fog and having increased activity due to fatigue over time, the increase in sensitivity and the increase in sand fog are also improved.

Example 2 To the emulsion prepared in Example 1, the tetrazaindene compounds of the present invention and comparative examples shown in Table 2 were added at 8 × 10 ₋₄ mol / mol A.
5 g of the compound of the present invention was added as a hydrazine compound, or 5 × 10 ⁻⁴ mol / mol of Ag was added, and 10 kinds of samples shown in Table 2 were prepared according to the method of Example 1. The sample was exposed and developed in the same manner as in Example 1 to determine the sensitivity and gamma. The sand fog test and evaluation were also performed in the same manner as in Example 1. The tetrazaindene compounds of Comparative Examples tested are shown below.

[0151]

[Chemical 100]

[0152]

[Table 2]

From the results shown in Table 2, the photographic light-sensitive material of the present invention is similar to the photographic light-sensitive materials of Comparative Examples in that a developer having the same high sensitivity and high contrast as that of the developer which has increased activity due to fatigue over time is used. The increase in sensitivity and the increase in sand fog have also been improved.

[0154]

The combination of the hydrazine compound and the tetrazaindene compound of the present invention provides extremely high contrast, high sensitivity and less sand fog by rapid development processing using a stable developer having a high sulfite ion concentration. In addition, a silver halide light-sensitive material having improved sensitivity and increased sand fog can be obtained with a developer having increased activity due to fatigue over time.

Claims (1)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer, and the silver halide emulsion layer or another hydrophilic colloid layer containing a compound represented by the following chemical formula 1. A silver halide photographic light-sensitive material, characterized in that the silver halide emulsion layer contains at least one compound represented by the following formula (2). [Chemical 1] [In Chemical Formula 1, Ar represents an aryl group, and R is -OR ₁
Or a group represented by —N (R ₂ ) (R ₃ ). R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted unsaturated heterocyclic group, or a substituted or unsubstituted aryl group. R ₂ and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted unsaturated heterocyclic group, or a substituted or unsubstituted pyridinium group. .. R ₂ and R ₃ may be linked to each other to form a ring. ] [Chemical 2] [Wherein R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or an alkylthio group, and R ₄ And R ₅ may together form a 5- or 6-membered ring. However, the total number of carbon atoms of R ₄ and R ₅ is 3 or more. R ₇ represents a hydroxy group or a mercapto group. ]