JPH06273879A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material ensuring very high contrast, high sensitivity and improved sandy fog by rapid development with a stable developing soln. having a high sulfite ion concn. CONSTITUTION:This silver halide photographic sensitive material contains a hydrazine deriv. and at least one of compds. represented by formulae I, II, wherein each of R<1>, R<2>, R<5>-R<7> and R<10> is alkyl, aralkyl or alkenyl, each of R<3>, R<4>, R<8>, R<9>, R<11> and R<12> is H, alkyl, aralkyl, alkenyl or aryl, each of L<1>-L<17> is methine, each of Z<1>-Z<6> is a group of atoms required to form a 5- or 6-membered N-contg. hetero ring, X<-> is an acid anion and each of (m) to (u) is 0 or 1 but (o) and (t) are not simultaneously 0.

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 with 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 (Use of hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 No. 2,419,975 (containing β-monophenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers)
No. and Mees "The Theory of Photographic pro
cess ”, 3rd edition (1996), page 281 and the like.

Among these, especially US Pat. No. 2,41
No. 9,975, it is disclosed that a high contrast negative image is obtained by adding a hydrazine compound. That is, it is described that when a hydrazine compound is added to a silver chlorobromide emulsion and development is performed with a developing solution having a high pH of 12.8, extremely high photographic characteristics with a gamma (γ) exceeding 10 are obtained. There is.

However, a strong alkaline developing solution having a pH close to 13 is easily oxidized by air and is unstable, and a halftone image (dot im) which is useful for printing plate making regardless of whether it is a negative image or a positive image.
It is extremely useful for photographic reproduction of continuous tone images or reproduction of line drawings.

For this 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 The method of developing with a hydroquinone developer (0.1 mol / l or less) was generally used. (Squirrel development)

However, according to this method, since the sulfite ion in the developing solution is low, the developing solution is extremely unstable and cannot be stored for more than 3 days. Further, 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 super-high 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,
No. 977, No. 4,224,401, No. 4,24
No. 3,739, No. 4,269,929, No. 4,2
Nos. 72,614 and 4,323,643 describe a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound, which has a pH of 11.0 to 1.
In 2.3, a system was proposed, which contains 0.15 mol / l or more of a sulfite preservative and is processed with a developer having good storage stability to form an extremely hard negative image. In this new image forming system, conventional lith development could use only silver chlorobromide with a high silver chloride content.
It is characterized in that it can be used with silver iodobromide or silver chloroiodobromide.

[0009] However, these image forming systems using hydrazine have a markedly high image-sensitivity and at the same time innumerable circular fog (sand fog) due to infectious development in the unexposed portion is apt to occur, resulting in remarkable image quality. This is a serious problem in the photomechanical process because it impairs the photolithography process.

On the other hand, various light sources (for example, LED, Ar laser, He) are used for exposing silver halide photographic light-sensitive materials.
-Ne laser and semiconductor laser) have been developed and put to practical use, and silver halide photographic light-sensitive materials are required to have optimum spectral sensitivity to these light sources depending on the purpose of use. As one of the technologies for such a silver halide photographic light-sensitive material, various types of cyanine dyes and merocyanine dyes are added to a silver halide photographic emulsion, and the wavelengths longer than the unique light-sensitive wavelength range of the silver halide are used. It is generally well known that, in the wavelength region, the sensitivity in a specific wavelength region is extremely effectively increased.

In the above-mentioned image forming system using a hydrazine derivative to obtain ultra-high contrast photographic characteristics using a stable developing solution, a cation-based compound (Japanese Patent Application Nos. 58-24891 and 60-9347) provides high sensitivity, It is known that high contrast is promoted.

[0012]

However, the system using the hydrazine derivative and the cationic dye has a problem that sand fog easily occurs, which is not preferable in the photomechanical process. Therefore, great efforts have been made to improve sand fog by using a cationic dye as a spectral sensitizing dye, but it is still not sufficient.

Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a photographic characteristic having a very high contrast and a high γ of more than 10 using a stable developing solution. Is. Secondly, the 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.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to have at least one light sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer or other hydrophilic colloid layer is hydrazine. A silver halide photographic light-sensitive material containing a derivative, wherein the silver halide emulsion layer contains at least one compound represented by the following chemical formulas 1 and 2 Achieved

In the formula, R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R
¹⁰ is an alkyl group (for example, a lower alkyl group such as methyl, ethyl, propyl and butyl, a hydroxyalkyl group such as β-hydroxyethyl and γ-hydroxypropyl, an alkoxyalkyl group such as β-methoxyethyl and γ-methoxypropyl) , Β-acetoxyethyl, γ-acetoxypropyl, β-benzoyloxyethyl and other acyloxyalkyl groups, carboxymethyl, β-carboxyethyl and other carboxyalkyl groups, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl, etc. An alkoxycarbonylalkyl group,
β-sulfoethyl, γ-sulfopropyl, δ-sulfobutyl and other sulfoalkyl groups), aralkyl groups (for example,
Benzyl, phenethyl, sulfobenzyl, etc.) and alkenyl groups (eg, allyl), R ³ , R ⁴ , R ⁸ , R
⁹ , R ¹¹ and R ¹² are a hydrogen atom and an alkyl group (R
^{1, R 2, R 5,} R 6, R 7, when the R ¹⁰ as defined), an aralkyl group ^{(R 1, R 2, R} 5, R 6, R 7, when the R ¹⁰ as defined), an alkenyl group (R ¹ , R ² , R ⁵ , R ⁶ ,
R ⁷ and R ^{10 have} the same meaning), and an aryl group (eg, phenyl, tolyl, methoxyphenyl, chlorophenyl, carboxyphenyl, naphthyl, etc.).

L1 to L17 each represent a methine group. The methine group is an alkyl group (R ¹ , R ² , R ⁵ , R ⁶ , R
⁷ , synonymous with R ¹⁰ ), aryl group (R ³ , R ⁴ , R
⁸ , R ⁹ , R ¹¹ and R ¹² ) and an alkoxy group (methoxy, ethoxy, propoxy, butoxy, etc.) may be substituted, and further 5 or 6 may be linked to each other.
It may form a member ring.

Z ^{1 to} Z ⁶ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Specific examples of Z ¹ (for convenience, indicated by the name of the starting material tertiary base) include, for example, a benzoxazole ring, a naphthoxazole ring,
There are benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, quinoline ring, benzoquinoline ring, indolenine ring, benzoindolenine ring, benzimidazole ring, naphthimidazole ring, Z ³ , Z ⁶ As specific examples of, in addition to the examples described in Z ¹ , examples of Z ³ when o is 0 and examples of Z ⁶ when t is 0 are an oxazoline ring, an oxazole ring, a thiazoline ring, Examples thereof include a thiazole ring and a pyridine ring. These heterocyclic ring and condensed benzene ring or naphthalene ring may be an alkyl group, an aryl group, an alkoxy group, a hydroxy group, a carboxy group, an alkoxycarbonyl (for example, methoxycarbonyl, ethoxycarbonyl, etc.), a halogen atom ( For example, it may have a substituent such as chlorine and bromine).
Further, specific examples of the nitrogen-containing heterocycle formed by Z ² include a 2-thioxoimidazolidine ring, a 2-thioxooxazolidine ring, a 2-thioxothiazolidine ring and the like, which are formed by Z ⁴ and Z ⁵ . Specific examples of the nitrogen-containing heterocycle include an oxazolidine ring, a thiazolidine ring and an imidazolidine ring.

An example of the nitrogen substituent of the nitrogen-containing heterocycle formed by Z ² , Z ⁴ and Z ⁵ is an alkyl group (R
^{1, R 2, R 5,} R 6, R 7, when the R ¹⁰ as defined), an aralkyl group ^{(R 1, R 2, R} 5, R 6, R 7, when the R ¹⁰ as defined), an aryl group (R ³ , R ⁴ , R ⁸ , R ⁹ , R
¹¹ , synonymous with R ¹² ), a heterocyclic residue (eg, 2-pyridyl group, 2-thiazolyl group) and the like.

X-is an acid anion (eg methylsulfate,
Alkylsulfate ion such as ethylsulfate, thiocyanate ion, toluenesulfonate ion, chlorine, bromine, iodine,
Halogen ion, perchlorate ion, etc.), m,
n, o, p, q, r, s, t, u are 0 or 1 respectively
, But o and t are never 0 at the same time. Next, of the sensitizing dyes represented by Chemical Formulas 1 and 2 of the present invention, typical examples will be given, but the scope of the present invention is not limited thereto.

[0020]

[Chemical 3]

[0021]

[Chemical 4]

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

When the compound of the present invention is contained in a photographic light-sensitive material, it can be mixed with an organic solvent such as methanol, ethanol, acetone, cellosolve, pyridine, dimethylacetamide, dimethylformamide, etc. It can be added to the silver halide emulsion alone or as a solution of a mixed solvent, or can be dispersed and added to the silver halide emulsion as solid grains.

When these compounds are added to the silver halide emulsion, they may be added at any time during the emulsion production process, but it is generally preferable to add them after the completion of chemical ripening. The addition amount varies depending on the type of compound or the type of silver halide emulsion, but is 1 in terms of silver nitrate.
A wide range of approximately 4-1200 mg per 00 g can be used.

The hydrazine derivative used in the present invention includes hydrazine sulfate, hydrazine hydrochloride and the like, and US Pat. Nos. 4,224,401 and 4,243,734.
Nos. 4,272,614 and 4,385,10
No. 8, No. 4,269,929, No. 4,323,6
No. 43, No. 4,988,604, No. 4,994,
365 and JP-A-56-106244 and 61-2.
No. 30145, No. 61-267759, No. 62-27
0953, 62-178246, 62-180.
No. 361, No. 62-275247, No. 63-2533.
57, JP-A Nos. 2-841, 2-8834 and 3
There are hydrazine derivatives and the like described in the specifications such as -184039 and 4-15642, which can be used in the present invention.

Typical examples of the hydrazine derivative are shown below, but the scope of the present invention is not limited to these.

[0044]

[Chemical formula 23]

[0045]

[Chemical formula 24]

[0046]

[Chemical 25]

[0047]

[Chemical formula 26]

[0048]

[Chemical 27]

[0049]

[Chemical 28]

[0050]

[Chemical 29]

[0051]

[Chemical 30]

[0052]

[Chemical 31]

[0053]

[Chemical 32]

[0054]

[Chemical 33]

[0055]

[Chemical 34]

[0056]

[Chemical 35]

[0057]

[Chemical 36]

[0058]

[Chemical 37]

[0059]

[Chemical 38]

[0060]

[Chemical Formula 39]

[0061]

[Chemical 40]

[0062]

[Chemical 41]

[0063]

[Chemical 42]

[0064]

[Chemical 43]

[0065]

[Chemical 44]

[0066]

[Chemical formula 45]

[0067]

[Chemical formula 46]

[0068]

[Chemical 47]

[0069]

[Chemical 48]

[0070]

[Chemical 49]

[0071]

[Chemical 50]

[0072]

[Chemical 51]

[0073]

[Chemical 52]

[0074]

[Chemical 53]

[0075]

[Chemical 54]

[0076]

[Chemical 55]

The hydrazine derivative 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 hydrazine derivative in the layer depends on the characteristics of the silver halide emulsion used, the structure of the compound and the development conditions, the appropriate content can vary over a wide range, A range of about 10 ^-6 to 10 ^-2 moles per mole of silver is practically useful, more preferably a range of 10 ^-5 to 10 ^-2 moles.

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. When silver or silver iodobromide 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 which has been physically ripened is preferably coated with necessary additives after desalting, but the desalting treatment can be omitted.

The silver halide emulsion used in the present invention is
It can be chemically aged by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine and rhodanine, and US Pat. Nos. 1,574,944 and 2,278,947.
No. 2,410,689, No. 2,440,20
No. 6, No. 3,187,458, No. 3,415,6
Sulfur-containing compounds as described in No. 49, No. 3,501,313 and the like can be used. In addition to sulfur sensitization, U.S. Pat. Nos. 2,448,060 and 2,
540,086, 2,556,245, 2,566,263 described in combination with a sensitizing method using a salt of a noble metal such as platinum, palladium, iridium, rhodium, ruthenium. Can be used. Further, a sensitizing method using various gold compounds such as potassium chloroaurate and auric chloride and palladium compounds such as palladium chloride can be used in combination.

The photosensitive material of the present invention may be provided with an overcoat layer, an intermediate layer, a backcoat layer, an undercoat layer and other hydrophilic colloid layers in addition to the photosensitive emulsion. Furthermore, a matting agent may be contained in these layers.

As the binder or protective colloid which 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. Sex colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , A partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone,
It is possible to use various synthetic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and the like. As the gelatin, other than lime-processed gelatin, acid-processed gelatin or acid-processed gelatin as described in Bull.Soc.Sci.Phot.Japan, No.16, P30 (1966) may be used. A hydrolyzate or an enzymatic hydrolyzate thereof can also be used.

The photographic emulsion used in the present invention includes, for example, known stabilizers such as mercaptotetrazoles, mercaptotriazoles, benzotriazoles and benzimidazoles, antifoggants, polyalkylene oxides, thioether compounds and quaternary compounds. Various development accelerators such as ammonium salt compounds, and further US Pat. No. 4,975,3
54, 5,126,227, JP-A-62-25.
0439, 63-124045, JP-A-2-97.
It is also possible to contain a compound which promotes high contrast as described in No. 939.

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 and the like) can be used alone or in combination.

Further, the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may be coated with a coating aid,
A surfactant may be included for various purposes such as antistatic, improvement of slipperiness, emulsion dispersion, prevention of adhesion and improvement of photographic characteristics (for example, development acceleration, hardening, sensitization). For example, saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic interface containing carboxylic groups such as ionic surfactants, alkyl carboxylates, alkyl sulfates, alkyl phosphates, etc., and acidic groups such as sulfo, phospho, sulfate, phosphate, etc. Activators, amino acids, aminoalkyl sulfonic acids, amphoteric surfactants such as aminoalkyl sulfates or phosphoric acid esters, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer 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,
Monomer components such as vinyl acetate, acrylonitrile, olefin, styrene, etc., or a combination thereof with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid, etc. The polymer can be used.

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

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 high pH 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 a sufficient amount of sulfite ions (especially 0.15 mol / l or more) as a preservative can be used, and a pH of 9.5 or more, particularly, 10.5-12.3
With the developer described above, a sufficiently super negative tone image can be obtained. The developing agent is not particularly limited, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination.
Other developers include alkali metal sulfites, carbonates,
Includes a pH buffer such as borate and phosphate, a bromide, an iodide, and a development inhibitor such as an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant be able to. 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-5. -Sulfonic acids) and the like. Specific examples of these additives are described in Research Disclosure 176, Item 17643 and the like.

In the present invention, a system may be adopted in which a developing agent is incorporated in the light-sensitive material and the processing is carried out with an alkaline activator solution. (JP-A-57-129433,
57-129434, 57-129435, 5
7-129436, 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 time from putting the light-sensitive material in the automatic developing machine until it comes out is set to 60 to 120 seconds, it is possible to obtain a super photographic negative tone gradation photographic characteristic. The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description.

[0092]

【Example】

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% so that the silver iodide was distributed evenly throughout the grain.

This emulsion was subjected to sulfur sensitization by a conventional method and then 1
-Phenyl-5-mercaptotetrazole was added, and this was divided and the compounds of the present invention and the comparative compound were added as sensitizing dyes as shown in Table 1 to give the hydrazine compound of formula 29 at 5 * 10 <-4> mol / mol. Addition of mol Ag, 5-methylbenzotriazole, 2-hydroxy 4,6-dichloro-
After adding 1,3,5-triazine sodium salt and sodium dodecylbenzene sulfonate, silver nitrate was coated on the polyethylene terephthalate film so that the silver content was 5 g / m 2 and the gelatin was 3 g. On top of this, as a protective layer, 1 g / m 2 of gelatin, and a surfactant, a matting agent,
A hardener was added and applied to prepare the samples shown in Table 1. The sensitizing dyes of the comparative examples tested are shown below.

[0094]

[Chemical 56]

[0095]

[Chemical 57]

[0096]

[Chemical 58]

[0097]

[Chemical 59]

[0098]

[Chemical 60]

[0099]

[Chemical formula 61]

Each of the samples thus obtained was exposed and developed to measure the sensitivity value. A xenon lamp was used for exposure, and exposure was performed for 10 −4 seconds through an interference filter having a transmitted light peak at 633 nm. Sensitivity value is transmission density 3.
The amount of exposure required to obtain 2 was obtained, and Table 1 shows the relative values when the sensitivity value of the sample of the comparative example is 100. Further, gamma is represented by tan θ in the linear portion where the optical density is 1.0 to 2.5. Development is performed with the developer of the following composition 38
It was developed at 20 ° C. for 20 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.

<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-Mercaptobenzimidazole-5-sulfonic acid 0.2 g 3- (5-Mercaptotetrazole) benzene sodium sulfonate 0.2 g N-n-butyldiethanolamine 12.0 g sodium toluenesulfonate 8.0 g Water was added and the pH was adjusted to 11.5 with 1 l potassium hydroxide.

[0103]

[Table 1]

From the results shown in Table 1, the photographic light-sensitive material of the present invention can obtain a high-sensitivity and high-contrast image as compared with the photographic light-sensitive material of Comparative Example, and the generation of sand fog is also improved.

Example 2 The emulsion prepared in Example 1 was supplemented with 2.10 as a sensitizing dye.
5 × 10 ⁻⁵ mol / mol Ag was added, the compound shown in Table 2 was added as a hydrazine compound at 5 × 10 ⁻⁴ mol / mol Ag, and a sample was prepared according to the method of Example 1 below. 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.

[0106]

[Table 2]

From the results shown in Table 2, the photographic light-sensitive material of the present invention can obtain a high-sensitivity and high-contrast image as compared with the photographic light-sensitive material of Comparative Example, and there is no problem in the occurrence of sand fog.

[0108]

EFFECTS OF THE INVENTION According to the present invention, an extremely high contrast can be obtained by a rapid development process using a developer having a high sulfite ion concentration.
A silver halide photographic light-sensitive material having high sensitivity and improved sand fog can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer or another hydrophilic colloid layer. , At least one compound represented by the following chemical formulas 1 and 2 in the silver halide emulsion layer.
A silver halide photographic light-sensitive material characterized by containing two. [Chemical 1] [Chemical 2] [Wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ¹⁰ represent an alkyl group, an aralkyl group and an alkenyl group, respectively, and
³ , R ⁴ , R ⁸ , R ⁹ , R ¹¹ , and R ¹² each represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, or an aryl group. L ^{1 to} L ¹⁷ each represent a methine group. Z
^{1 to} Z ⁶ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. X- represents an acid anion,
m, n, o, p, q, r, s, t, and u each represent 0 or 1, but o and t are not 0 at the same time. ]