JPH06110147A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress an increase of fogging at the time of preservation at high temperature and the generation of 'black spots' in unexposed parts by incorporating a nucleation accelerator into the above material and incorporating at least one kind of specific compds. into a silver halide emulsion. CONSTITUTION:This silver halide photographic sensitive material contains the nucleation accelerator in silver halide emulsion layers and/or other hydrophilic colloidal layers and the silver halide emulsion contains at least one kind of the compds. expressed by formula. In the formula, R<1> denotes a sulfoaralkylene group, sulfoalkenyl group, etc., R<2>, R<3> and R<4> respectively denote an alkyl group, alkenyl group, aryl group, etc., and these groups may arbitrarily have substituents. V<1> and V<2> respectively denote an alkyl group, alkoxy group, halogen atom, etc. L<1> and L<2> respectively denote a methyl carbon and may be substd. with an alkyl group, alkoxy group, aralkyl group or aryl group. The silver halide emulsion consists of the silver halide contg. 55 to 100mol% silver bromide.

Description

Detailed Description of the Invention

The present invention relates to a photographic light-sensitive material having a silver halide light-sensitive layer on a support, and more particularly to a photographic light-sensitive material capable of obtaining high contrast.

[0002]

BACKGROUND OF THE INVENTION The photomechanical process involves the conversion of continuous-tone originals into halftone images. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The lith-type silver halide photographic light-sensitive material used for infectious development has, for example, an average particle size of 0.2 μm, a narrow particle distribution, a well-shaped particle, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion. By processing the lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, an image having high contrast, high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
It is difficult to keep the development quality constant during continuous use. There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in JP-A-56-106244, a silver halide photographic light-sensitive material containing a hydrazine derivative is treated with an alkali developing solution. According to these methods, it is possible to obtain a high-contrast image even by processing with a developer which has good preservative property and can be processed rapidly.

In these techniques, in order to fully exert the high contrast property of the hydrazine derivative, the hydrazine derivative had to be treated with a developer having a pH of 11.2 or higher. A high pH developer having a pH of 11.2 or higher is more stable than a lith developer when exposed to air, and is more stable than a lith developer. However, due to the oxidation of the developer, a super-high contrast image may not often be obtained. .

In order to make up for this drawback, JP-A 63-29751, JP-A 1-179939, JP-A 1-179940 and US Pat. A silver halide photographic light-sensitive material containing a high-contrast hydrazine derivative and a nucleation accelerator is disclosed.

On the other hand, in recent years, silver halide photographic light-sensitive materials recorded by a laser light source have been frequently used in the field of printing plate making. Known light sources include an Ar laser having an output wavelength of 488 nm, a HeNe laser having an output wavelength of 632.8 nm, a light emitting diode (LED) having an output wavelength of 650 to 700 nm, and a red semiconductor laser having an output wavelength of 670 to 680 nm. There is. From the viewpoint of ease of use, it is advantageous that the photosensitive material used in the exposure apparatus having these light sources can be handled under bright safe light. As a silver halide photographic light-sensitive material recorded by a laser light source, a high-sensitivity emulsion color-sensitized with a sensitizing dye so as to have optimum sensitivity to these light sources is used.

However, a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator, which gives a high contrast even in a developer having a relatively low pH as described above, uses the above-described color-sensitized and high-sensitivity emulsion. Fog increased during storage, especially at high temperature, and sand-like fine spots called "black spots" were generated in the unexposed areas peculiar to photosensitive materials using hydrazine derivatives, causing sensitivity fluctuations. It was something that

[0009]

In view of the above problems, the object of the present invention is to suppress the rise of fog and the occurrence of "black spots" in the unexposed area during storage, especially at high temperature storage, and to reduce the sensitivity fluctuation. It is to provide a silver halide light-sensitive material.

[0010]

The above object of the present invention can be achieved by either of the following configurations (1) and (2).

(1) In a silver halide photographic light-sensitive material containing a hydrazine derivative in at least one silver halide emulsion layer and / or other hydrophilic colloid layer on a support, the silver halide emulsion layer and / or Alternatively, the nucleation accelerator is contained in the other hydrophilic colloid layer, and the silver halide emulsion has the following general formula [D-1] or general formula [D-
2], a silver halide photographic light-sensitive material containing at least one compound represented by the general formula [D-3], the general formula [D-4] or the general formula [D-5].

[0012]

[Chemical 2]

In the formulas [D-1] to [D-3], R ¹ is a sulfoaralkylene group, a sulfoalkenyl group,-(Cm ¹ H ₂ m ₁ O) lCm ² H ₂ m ² SO ₃ M ¹ group (m ¹ and m ² each represent 2 to 4, 1 represents 1 to 2 and M ¹ represents a hydrogen atom or an alkali metal atom), a sulfatoalkyl group or a carboxyalkyl group. R ² , R ³ and R
Each of ⁴ represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups can optionally have a substituent. V ¹ and V ² are each an alkyl group, alkoxy group, halogen atom, cyano group, carboxy group, alkoxycarbonyl group, trifluoromethyl group, aryl group, sulfonamide group, acyl group, amide group, sulfamoyl group, carbamoyl group or Represents a hydrogen atom.

L ¹ and L ² each represent a methine carbon and may be substituted with an alkyl group, an alkoxy group, an aralkyl group or an aryl group. L represents a methylene chain having 2 to 6 carbon atoms, and M represents a hydrogen atom or an alkali metal atom.

In the general formula [D-2], V ³ and V ⁴ are the same as V ¹ and V ² , respectively, but one of V ³ and V ⁴ is an alkoxycarbonyl group, a sulfonamide group,
It is a group selected from an acyl group, an amide group, a sulfamoyl group, a carbamoyl group or an alkoxy group.

In the general formula [D-3], R ⁵ , R ⁶ and R ⁷ are the same as R ² , R ³ and R ⁴ , respectively, but at least one of R ⁵ , R ⁶ and R ⁷ is an aryl group. , A heterocyclic group, an aralkyl group, or an alkenyl group.

In the general formula [D-4], Z ¹¹ represents a non-metal atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring excluding the imidazole ring, and R ¹¹ is a sulfoalkyl group or sulfoaral. Xylene group carboxyalkyl group or-(Cm ¹
It represents an _{^{H 2 m 1 O) lCm 2}} H 2 m 2 SO 3 M 1 group. R ¹² , R ¹³ and R ¹⁴
Are the same as R ² , R ³ and R ⁴ , respectively, and L ¹¹ and L
¹² is the same as L ¹ and L ² , respectively, and n ₁₁ is 0 or 1
Represents

In the general formula [D-5], Z ²¹ is 5 member, 6
Represents a non-metal atomic group necessary for forming a nitrogen-containing heterocyclic ring, R ²¹ is the same as R ¹¹ , R ²² , R ²³ and R ²⁴ are the same as R ² , R ³ and R ⁴ , respectively. Yes, L ²¹ , L ²² , L
²³ and L ²⁴ are the same as L ¹ and L ² , respectively, and n ₂₁
Represents 0 or 1.

(2) 55 to 100 mol% of silver halide emulsion
The silver halide photographic light-sensitive material according to (1) above, which comprises the silver halide containing silver bromide.

The present invention will be described in detail below.

In the photosensitive dyes represented by the general formulas [D-1] to [D-5] according to the present invention, specific examples of the sulfoaralkylene group represented by R ¹ , R ¹¹ and R ²¹ are shown.
Groups such as o-sulfobenzyl, p-sulfobenzyl, p-sulfophenethyl and the like, and specific examples of the carboxyalkyl group include groups such as carboxymethyl and carboxyethyl,-(Cm ¹ H ₂ m ¹ O ) Specific examples of the lCm ² H ₂ m ² SO ₃ M ¹ group include groups such as 6-sulfo-3, oxahexyl, 7-sulfo-3-oxaheptyl, 9-sulfo-3,6-dioxanonyl and the like. To be

Specific examples of the sulfoalkenyl group represented by R ¹ include 3-sulfo-2-propenyl group, and specific examples of the sulfatoalkyl group include 3-sulfatopropyl,
Examples of the group include 2-sulfatoethyl, R ¹¹ and R ¹²
Specific examples of the sulfoalkyl group represented by include 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl and the like groups.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹² , R ¹³ ,
The alkyl groups represented by R ¹⁴ , R ²² , R ²³ and R ²⁴ include substituted and unsubstituted groups, such as methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl, carboxymethyl,
2-sulfoethyl, groups such as 3-sulfopropyl, and the like,
Specific examples of the alkenyl group include an allyl group, and specific examples of the aralkyl group include an unsubstituted group such as phenyl and naphthyl, and a substituted group such as p-carboxyphenyl, tolyl, and p-sulfophenyl. Specific examples of the heterocyclic group include unsubstituted groups such as pyridyl, furyl, thienyl and imidazolyl, and substituted groups such as chloropyridyl and carboxypyridyl.

Specific examples of the alkyl group represented by V ¹ , V ² , V ³ and V ⁴ include groups such as methyl and ethyl, and specific examples of the alkoxy group include groups such as methoxy and ethoxy. Specific examples of the halogen atom include fluorine, chlorine,
Examples of the alkoxycarbonyl group include groups such as ethoxycarbonyl and butoxycarbonyl, and examples of the aryl group include groups such as phenyl, tolyl, chlorophenyl, and sulfonamide. Specific examples of the group include groups such as methanesulfonamide and benzenesulfonamide, specific examples of the acyl group include groups such as acetyl and benzoyl, and specific examples of the amide group include acetylamino, benzoylamino and the like. Groups are mentioned, specific examples of the sulfamoyl group include groups such as sulfamoyl and dimethylsulfamoyl, and specific examples of the carbamoyl group include groups such as carbamoyl, dimethylcarbamoyl and morpholinocarbonyl.

Specific examples of the alkyl group substituted on the methine carbon represented by L ¹ , L ² , L ¹¹ , L ¹² , L ²¹ , L ²² , L ²³ and L ²⁴ include methyl, ethyl and butyl groups. Examples of the alkoxy group include groups such as methoxy and ethoxy, examples of the aralkyl group include groups such as benzyl and phenethyl, and examples of the aryl group include phenyl group. .

Specific examples of the alkali metal atom represented by M include atoms such as lithium, sodium and potassium.

The 5- or 6-membered nitrogen-containing heterocycle formed by Z ²¹ includes not only a monocycle but also a condensed ring, for example, oxazolidine, oxazoline, benzoxazoline, naphthoxazoline, thiazoline, benzothiazoline, naphthothiazoline. , Benzoselenazoline, naphthoselenazoline, benzimidazoline, naphthimidazoline, thiadiazoline, benzoterrazoline, and the like, and at any position on these rings, V ¹ , V ² , V ³ and V ⁴ It may have a substituent.

The general formula [D-1] to the general formula [D-
Typical specific examples of the photosensitive dye represented by [5] are shown below, but the invention is not limited thereto.

[0029]

[Chemical 3]

[0030]

[Chemical 4]

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

Next, the compounds of the hydrazine derivative used in the present invention are listed, but the present invention is not limited thereto.

For example, the hydrazine compound used in the present invention is represented by the following formula.

Ar-NHNH- (C = O) -R wherein R is a hydrogen atom or a blocking group, and Ar-NHNH- (C = O) -R
Represents an aryl group.

A hydrazine compound represented by the following formula is more preferable.

[0048]

[Chemical 18]

In the formula, R represents a hydrogen atom or a blocking group, and R ₁ represents a substituent. Further, R ₁ preferably has a diffusion resistance or a silver halide adsorption group. Specific examples include the compounds described in the following patents. JP-A-2-37
No. 2, No. 2-841, No. 2-947, No. 3-125434, No. 3-240036, No. 3-259240, and Japanese Patent Application No. 3-
No. 287997, No. 3-307934, No. 3-321988, No. 3-345207, No. 3-345817, No. 3-
No. 345819, No. 3-345820, No. 3-316796, No. 3-345818, No. 4-10268, No. 4-1
The compounds are described in the specifications of No. 3218 and No. 4-21322.

More specifically, the following hydrazine compounds may be mentioned.

[0051]

[Chemical 19]

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

Examples of the nucleation accelerator used in the present invention include amine compounds, hydrazine compounds, quaternary onium salt compounds and carbinol compounds, with amine compounds and carbinol compounds being preferred. Examples of these nucleation accelerators include those described in JP-A-4-56749, JP-A-63-124045 and JP-A-62-187340. These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule. Other specific examples include the compounds described in the following patents. Japanese Patent Application 3-29
Compounds described in 5926, 3-293366, 3-286619, 4-33451 and the like.

More specifically, the following nucleation accelerators are listed, but the present invention is not limited thereto.

As compounds described in JP-A-4-56949

[0059]

[Chemical formula 24]

[0060]

[Chemical 25]

[0061]

[Chemical formula 26]

And the like.

The silver halide emulsion used in the present invention (hereinafter referred to as "silver halide emulsion or simply emulsion") includes silver bromide containing 55 to 100 mol% of silver bromide, silver iodobromide,
Although silver chloroiodobromide and silver chlorobromide can be used, silver chloroiodobromide, silver bromide or silver iodobromide containing 3 mol% or less of silver iodide is preferable.

[(Standard deviation of particle size)] / (average value of particle size)
Monodisperse particles represented by × 100 and having a coefficient of variation of 15% or less are preferable.

Various techniques, additives and the like known in the art can be used in the silver halide emulsion of the present invention.

For example, in the silver halide photographic emulsion and backing layer used in the present invention, various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents,
A development inhibitor, an ultraviolet absorber, an anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer of the present invention.

As the support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, and polyolefin are coated. paper,
Examples thereof include glass and metal. These supports are subjected to a surface treatment if necessary.

More specifically, these additives are described in Research Disclosure Vol. 176 Item / 7643 (December 1978) and Vol. 187 Item / 8716 (November 1979),
The relevant parts are summarized below.

Additive Type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Stucking Agent, page 27 Id. To develop the silver halide photographic light-sensitive material of the present invention, for example, TH James, The Theory of the Photographic Process, Fourth Edition (The Theory of
the Photographic Process, Fourth Edition) No. 291-33
Page 4 and the Journal of the American Chemical Soci
ety) Volume 73, page 3,100 (1951), and the developers can be effectively used in the present invention.

These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination.

Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material of the present invention, the effect of the present invention is not impaired. Further, hydroxylamine or a hydrazide compound may be used as a preservative. In addition, it is possible to adjust the pH with a caustic alkali, an alkali carbonate, an amine or the like as used in a general black-and-white developer and to have a buffer function. The developer used in the present invention has a pH of 10.0 to 11.2.
Are preferred. If the pH is less than 10.0, the contrast becomes insufficient, and if the pH exceeds 11.2, black spots are significantly deteriorated.

In addition, the developer contains an inorganic development inhibitor such as bromcali and an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine and 1-phenyl-5-mercaptotetrazole. Agents, metal ion scavengers such as ethylenediamine tetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxides, sodium alkylaryl sulfonates, natural saponins, surface active agents such as sugars or alkyl esters of the above compounds Agent,
It is optional to add a hardening agent such as glutaraldehyde, formalin and glyoxal, and an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention may contain glycols such as diethylene glycol and triethylene glycol as an organic solvent. Further, it is preferable not to include the alkanolamines disclosed in JP-A-56-106244.

[0074]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per 1 mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The resulting emulsion was an emulsion consisting of cubic monodisperse grains (coefficient of variation 9%) having an average grain size of 0.20 μm. It was washed with water and desalted by a conventional method. The pAg at 40 ℃ after desalting is
It was 8.0. Subsequently, a 0.1 mol% aqueous solution of potassium iodide per mol of silver was added to this emulsion to convert the grain surface, and then a mixture of the compounds [A], [B] and [C] was added, followed by sulfur sensitization. To obtain Emulsion A.

[0076]

[Chemical 27]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was used, in which the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ^2.
And an emulsion protective layer of the following formulation (2) so that the amount of gelatin will be 1.0 g / m ^2, and on the other undercoat layer on the opposite side. Is a backing layer coated according to the following prescription (3) so that the amount of gelatin is 2.4 g / m ^2, and a backing protective layer of the following prescription (4) is further applied so that the amount of gelatin is 1 g / m ² . A sample was obtained by applying it to the.

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ² Sensitizing dye: General formula [D-1] to General formula of the present invention [D-5] Amount shown in Table 1 Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: Adenine 10 mg / m ² 1-phenyl-5 -Mercaptotetrazole 5mg / m ² Surfactant: Saponin 0.1g / m ²

[0079]

[Chemical 28]

[0080]

[Chemical 29]

Formulation (3) (backing layer composition)

[0082]

[Chemical 30]

Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² : S-1 6 mg / m ² Colloidal silica 100 mg / m ² Formulation (4) [Backing protective layer composition] Gelatin 1 g / m ² matting agent average particle size: 5.0μm monodisperse polymethyl methacrylate a cleat 50 mg / m ² surfactant: ^S-2 10mg / m 2 hardener: glyoxal 25 mg / m ^2: evaluation of H-1 35mg / m ² [photographic performance The obtained sample and a part of it were stored at 55 ° C. and 20% RH for 3 days as a substitute test for storability, and a wedge was adhered to the sample and exposed to Ar laser for 10 ⁻⁶ seconds to give the composition shown below. Processing was performed under the following conditions with an automatic processor GR-26SR for rapid processing manufactured by Konica Corp., in which the developing solution and the fixing solution described above were added.

The concentration of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the relative sensitivity was shown with the sensitivity of sample No. 1 no 2.5 being 100, and the tangent of density 0.1 and 2.5 was used to determine gamma. displayed. If the gamma value is less than 8.0, the contrast becomes insufficient and it cannot be used.

[Evaluation of black spots] The developed sample obtained above was visually evaluated in the unexposed area with a magnifying glass of 40 times. The highest rank is "5" when there are no black spots, and the rank is "4" according to the degree of occurrence of black spots.
"3", "2", and "1" and their ranks are sequentially lowered and evaluated. Ranks "2" and "1" are levels that are not practically preferable.

[Developer Composition 1] Potassium Sulfite Amount shown in Table 1 Hydroquinone 15.0 g 4-Methyl-4-hydroxymethyl-1phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 0.5 g Potassium carbonate 50.0 g Bromide Potassium 5.0 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.25 g 5-Methylbenzotriazole 0.4 g Water was added to make 1 liter, and the pH was adjusted to 10.6 with potassium hydroxide.

Fixer Formulation (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure water (Ion-exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 8.5 g When using the fixer, the above composition A in 500 ml of water is used. , Composition B were melted in this order and finished to 1 l for use. The pH of this fixer was adjusted to 4.8 with acetic acid.

[0088] The results are shown in Table 1.

[0089]

[Table 1]

As is clear from the results shown in Table 1, the present invention is superior to the comparative examples.

Example 2 A sample was obtained in the same manner as in Example 1 except that the silver halide emulsion was changed to the following silver halide emulsion B and the nucleation accelerator and the sensitizing dye of the present invention were changed as shown in Table 2. It was The obtained sample is Ar
Evaluation was performed in the same manner as in Example 1 except that the laser was changed to a HeNe laser for exposure.

The results are shown in Table 2.

[0093]

[Table 2]

As is clear from the results shown in Table 2, the present invention is superior to the comparative examples.

(Preparation of Silver Halide Emulsion B) Silver chloroiodobromide (35 mol% silver chloride, 0.5 mol% silver iodide) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 1 × 10 ^-6 mol per mol of silver. The obtained emulsion has an average grain size of 0.2.
The emulsion consisted of a 5 μm cubic monodisperse emulsion (variation coefficient 10%). This emulsion was desalted by a conventional method and then subjected to gold sulfur sensitization to obtain an emulsion B.

[0096]

According to the present invention, it is possible to provide a silver halide light-sensitive material which suppresses the rise of fog and the occurrence of "black spots" in the unexposed area during storage, particularly during storage at high temperature, and has little sensitivity variation. did it.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material containing a hydrazine derivative in at least one silver halide emulsion layer and / or other hydrophilic colloid layer on a support, said silver halide emulsion layer and / or Other hydrophilic colloid layers contain a nucleation accelerator, and the silver halide emulsion has the following general formula [D-1], general formula [D-2], general formula [D-3], general formula [D-4] and the general formula [D-
[5] A silver halide photographic light-sensitive material containing at least one compound represented by the formula [5]. [Chemical 1] [Wherein R ¹ in general formulas [D-1] to [D-3]
Is a sulfoaralkylene group, a sulfoalkenyl group,-(Cm ¹
H ₂ O) lCm ² H ₂ m ² SO ₃ M ¹ group (m ¹ and m ² each represent 2 to 4, 1 represents 1 to 2 and M ¹ represents a hydrogen atom or an alkali metal atom). Represents a sulfatoalkyl group or a carboxyalkyl group. R ² , R ³ and R ⁴ each represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups can have a substituent at any position. V ¹ and V ² are each an alkyl group, an alkoxy group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, a trifluoromethyl group, an aryl group, a sulfonamide group, an acyl group, an amide group, a sulfamoyl group, a carbamoyl group or Represents a hydrogen atom. L ¹ and L ² each represent a methine carbon and may be substituted with an alkyl group, an alkoxy group, an aralkyl group or an aryl group. L represents a methylene chain having 2 to 6 carbon atoms, and M represents a hydrogen atom or an alkali metal atom. In the general formula [D-2], V ³ and V ⁴ are each V ¹
The same as V ² and V ² , but one of V ³ and V ⁴ is a group selected from an alkoxycarbonyl group, a sulfonamide group, an acyl group, an amide group, a sulfamoyl group, a carbamoyl group or an alkoxy group. In formula [D-3], R ⁵ , R ⁶ and R ⁷ are the same as R ² , R ³ and R ⁴ , respectively, but at least one of R ⁵ , R ⁶ and R ⁷ is an aryl group or a heterocycle. A group selected from a group, an aralkyl group and an alkenyl group. General formula [D-
4], Z ¹¹ represents a non-metal atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring excluding the imidazole ring,
R ¹¹ represents a sulfoalkyl group, a sulfoaralkylene group, a carboxyalkyl group or a — (Cm ¹ H ₂ m ¹ O) lCm ² H ₂ m ² SO ₃ M ¹ group. R ¹² , R ¹³ and R ¹⁴ are R ² , R ³ and R ^{4 respectively.}
, L ¹¹ and L ¹² are the same as L ¹ and L ² , respectively, and n ₁₁ represents 0 or 1. General formula [D-5]
In Z ²¹ is 5-membered, represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic 6-membered, R ²¹ is as defined R ^11,
R ²² , R ²³ and R ²⁴ are respectively the same as R ² , R ³ and R ⁴ , L ²¹ , L ²² , L ²³ and L ²⁴ are respectively the same as L ¹ and L ² , and n ₂₁ is Represents 0 or 1. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion comprises silver halide containing 55 to 100 mol% of silver bromide. [Industrial applications]