JPH06118537A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material having high sensitivity, suppressing the occurrence of black spots and hardly undergoing a change in the sensitivity with the lapse of time after exposure because of satisfactory chemical sensitization. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on the base and contains a hydrazine deriv. in the emulsion layer or other hydrophilic colloidal layer. Part or all of a silver halide emulsion in the emulsion layer has been chemically sensitized in the presence of a polysulfide compd.

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 specifically, it has high sensitivity and little black spot
The present invention also relates to a silver halide photographic light-sensitive material which has little sensitivity fluctuation after exposure.

[0002]

BACKGROUND OF THE INVENTION It is known that certain silver halides can be used to form photographic images of extremely high contrast, and methods of forming such photographic images are used in the field of photolithography. For example, a lith-type silver halide light-sensitive material made of silver chlorobromide (at least a silver chloride content of 50% or more) is well known in the art, but it is theoretically impossible to increase the concentration of sulfurous acid, so that it is not susceptible to air oxidation. On the other hand, it had the drawback of being unstable.

For this reason, the instability of the image forming method by the developing method (lith development system) as described above is eliminated, and the image is developed with a processing solution having good storage stability, and an image having super high contrast photographic characteristics can be obtained. Forming system required, US patent
4,166,742, 4,168,977, 4,211,857, 4,22
4,401, 4,243,739, 4,272,606, 4,311,781
Surface latent image type silver halide photographic light-sensitive material added with a specific hydrazine compound as shown in No.
It has been proposed that a system containing a sulfite preservative in an amount of 0.15 mol / l or more and having a good storage stability is processed to form a super-high contrast negative image having a γ of more than 10. However, this new image forming system is extremely high contrast,
This causes an undesired phenomenon of black spots (glack pepper) due to infectious development, which is a problem in the photomechanical process. In particular, these black spots are likely to occur in the chemically ripened emulsion. In particular, when thiouretaa, seleureas, thiosulfates, thiazoles, and rhodanines are used as sulfur sensitizers, black spots are remarkably generated. As a result, chemical sensitization cannot be performed sufficiently. For example, as shown in JP-A-63-46437, chemical sensitization is performed only on low-sensitivity emulsions, or chemical sensitization is performed "shallow" to the extent that black spots do not occur. "To give" is often done. As described above, the chemical sensitization is not sufficiently performed, so that the sensitivity cannot be sufficiently enhanced, and the latent image generated by exposure is weak, so that the latent image is easily destroyed by moisture or oxygen in the air.

Further, when a highly active hydrazine represented by the general formula [H] is used, black spots are likely to occur, which has been an obstacle to practical use.

[0005]

OBJECTS OF THE INVENTION The first object of the present invention is to provide a silver halide light-sensitive material having high sensitivity and less black spots, and second, a light-sensitive material having a stable latent image and less sensitivity fluctuation after exposure. In offer.

[0006]

The above object of the present invention is to provide a silver halide having at least one photosensitive silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or other hydrophilic colloid layers. In a photographic light-sensitive material, a silver halide photographic light-sensitive material characterized in that a part or all of a silver halide emulsion in the emulsion layer is chemically sensitized in the presence of a polysulfide compound.

The hydrazine derivative is preferably a compound represented by the above general formula [H] (Formula 1).

The polysulfide compound referred to herein is an organic or inorganic compound having one or more sites where three or more sulfur atoms are linked in the present invention. As the polysulfide, any of linear, branched and cyclic compounds may be used, but a compound having a cyclic polysulfide group is particularly preferable from the viewpoint of stability of the polysulfide compound. Specific examples of these compounds include the following compounds. Of course, the present invention is not limited to this.

[0009]

[Chemical 2]

Regarding the timing of adding these compounds, they can be added in any step as long as the silver halide grains are chemically sensitized in the presence of a polysulfide compound. Specifically, chemical sensitization is performed before the formation of silver halide grains, during the formation of silver halide grains, before the completion of silver halide grain formation and before the desalting step, and after the desalting step and before the start of chemical sensitization. It may be at any time selected from the start of sensation and during chemical sensitization. Preferably, it is added at any time selected from the end of silver halide grain formation to before the desalting step, from after desalting to before the start of chemical sensitization, at the start of chemical sensitization and during chemical sensitization. . Of these, particularly good is at the start of chemical sensitization.

The addition amount of the polysulfide compound varies depending on the kind of silver halide emulsion to be applied and the magnitude of the expected effect, but is 1 × per mol of silver halide.
It is 10 ⁻⁵ mg to 100 mg. It is preferably 1 × 10 ^{−3 to} 10 mg.

In the chemical sensitization of the present invention, gold,
A sensitizing method using a precious metal such as platinum can be used together. Examples of these noble metal sensitizations include gold sensitization (US Pat. Nos. 2,540,085, 2,597,876, and 2,399,08).
No. 3, etc.), sensitization with Group VIII metal ions (US Pat. Nos. 2,448,060, 2,540,086, 2,566,245,
No. 2,566,263 and No. 2,598,079). In addition, in the present invention, ring sensitization (US Pat.
(518,698, 2,419,974, 2,983,610, etc.)
Can also be applied.

Next, preferred examples of the hydrazine derivative used in the present invention include the compounds represented by the above general formula [H] (Formula 1).

In the present invention, among these, the following general formula [Ha], [Hb], [Hc] or [H-] is further used.
The compound represented by d] is preferred.

[0015]

[Chemical 3]

In the above general formula [Ha], R ₁₁ and R ₁₂
Hydrogen atom, substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, butyl group, dodecyl group,
2-hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group), substituted or unsubstituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (for example, phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-
Methylcyclohexyl group, pyridyl group, 4-propyl-2-
Pyridyl group, pyrrolidyl group, 4-methyl-2-pyrrolidyl group) and the like, and R ₁₃ is a hydrogen atom, a substituted or unsubstituted benzyl group, an alkoxy group or an alkyl group (for example, benzyl group, p-methylbenzyl group, methoxy group). Group, an ethoxy group, an ethyl group, a butyl group), R ₁₄ and R ₁₅ each represent a divalent aromatic group (eg, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents L. A divalent linking group (for example, —SO ₂ CH ₂ CH ₂ NH—, —S
_{O 2 NH -, - OCH 2} SO 2 NH -, - O -, - CH = N-) represents,
R ₁₆ represents —NR′R ″ or —OR ₁₇ , and R ′, R ″ and R ₁₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, dodecyl group), phenyl group ( For example, phenyl group, p-methylphenyl group, p-
Methoxyphenyl group), naphthyl group (eg α-naphthyl group, β-naphthyl group) or heterocyclic group (eg unsaturated heterocyclic group such as pyridine, thiophene, furan or saturated heterocyclic group such as tetrahydrofuran, sulfolane) And R ′ and R ″ may form a ring (for example, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

M and n each represent 0 or 1.
When R ₂₈ represents —OR ₂₉ , Y preferably represents a sulfur atom.

[0018]

[Chemical 4]

In the formula, R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a 3-aryloxypropyl group), a substituted or unsubstituted phenyl group or a naphthyl group. , Cyclohexyl group, pyridyl group, pyrrolidyl group, substituted or unsubstituted alkoxy group (eg methoxy group, ethoxy group, butoxy group)
Alternatively, it represents a substituted or unsubstituted aryloxy group (eg, phenoxy group, 4-methylphenoxy group).

In the present invention, R ₂₃ is preferably a hydrogen atom or an alkyl group.

R ₂₄ represents a divalent aromatic group (eg, phenylene group, naphthylene group), and Z represents a sulfur atom or an oxygen atom.

R ₂₅ is a substituted or unsubstituted alkyl group,
It represents an alkoxy group or an amino group, and examples of the substituent include an alkoxy group, a cyano group and an aryl group.

The hydrazine derivative can be easily synthesized by a known method. For example, JP-A-2-214850.
No. 2, No. 2-47646, No. 2-12237 and the like.

Representative compounds represented by the above general formulas [Ha-] and [H-b] are shown below.

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or represents a heterocyclic oxy group, R ₃₁ and R
₃₂ may form a ring with a nitrogen atom. When n = 2,
R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or hetero. Represents a ring oxy group. However, when n = 2, R ₃₁ and R
_At least one of ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. R ₃₃ represents an alkynyl group or a saturated heterocyclic group.

The compound represented by the general formula [Hc] or [Hd] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.). Represents

R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl). Etc.), an alkynyl group (eg, propargyl, butynyl, pentynyl, etc.),
Aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, unsaturated heterocyclic groups such as pyridine, thiophene, furan and saturated heterocyclic groups such as tetrahydrofuran, sulfolane),
Hydroxy group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, ,
Phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), and when n = 1, R ₃₁ and R ₃₂ together with the nitrogen atom form a ring (eg, piperidine, piperazine, morpholine, etc.) May be formed.

However, when n = 2, at least one of R ₃₁ and R ₃₂ is an alkenyl group, alkynyl group, saturated heterocyclic group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or hetero. It represents a ring oxy group.

Specific examples of the alkynyl group and saturated heterocyclic group represented by R ₃₃ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

In each general formula, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in non-moving photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercapto heterocyclic group and triazole group.

--NH in the general formulas [Hc] and [Hd]
H of NH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg acetyl, trifluoroacetyl,
Ethoxycarbonyl, etc.), an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.) and the like, and the compounds represented by the general formulas [Hc] and [Hd] are such compounds. Also includes.

More preferred compounds in the present invention are the compounds of the general formula [Hc] when n = 2, and the compounds of the general formula [Hd].

In the compound of the general formula [Hc] for n = 2, R ₃₁ and R ₃₂ are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, saturated or unsaturated heterocyclic group, hydroxy group, Or an alkoxy group, and R ₃₁
Further, a compound in which at least one of R ₃₂ and R ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is more preferable.

Typical compounds represented by the above general formulas [Hc] and [Hd] are shown below.
However, as a matter of course, the specific compounds of the general formulas [Hc] and [Hd] that can be used in the present invention are not limited to these compounds.

Specific compound examples

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

Specific compounds other than the above are disclosed in
2-841 542 (4) to 546 (8) compound examples
There are (1) to (61) and (65) to (75).

The hydrazine derivative in the present invention is disclosed in
It can be synthesized by the method described in No. 2-841, pages 546 (8) to 550 (12). The addition position of the hydrazine derivative of the present invention is the silver halide emulsion layer and / or the adjacent layer. The addition amount is preferably 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver, and more preferably 1 × 10 ^-5 mol to 1 per mol of silver.
× 10 ^-2 mol.

When [Hc] or [Hd] is contained as a hydrazine derivative, it is described in JP-A-4-98239, page (7), lower left column, line 1 to page (26), lower left column, line 11. It is preferred that at least one of the nucleation promoting compounds is contained in the silver halide emulsion layer and / or the non-photosensitive layer on the side of the silver halide emulsion layer on the support.

The following are typical examples of the nucleation accelerator.

[0055]

[Chemical 17]

[0056]

[Chemical 18]

Still another specific example is JP-A-4-98239.
No. (8) pages-72 compounds I-1 to I-26,
Compounds II-1 to II-29 described on pages (9) to (10),
Compounds III-1 to III-2 described on pages (10) to (11)
5, Compounds IV-1 to IV-4 described on pages (11) to (13)
1, compounds VI-1 to VI described on pages (13) to (14)
-27, Compounds V-II-1 to 1 described in pages (15) to (16)
V-II-30, Compound V-III described on pages (16) to (17)
-1 to V-III-35, compounds described on pages (18) to (20)
VI-I-1 to VI-I-44, compounds described on pages (21) to (24) VI-II-1 to VI-II-68 and described on pages (24) to (26) Among the compounds VI-III-1 to VI-III-35 which have been described, there are those other than the representative examples mentioned above.

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support. The silver halide emulsion can be coated directly on the support or can be coated through another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the emulsion layer. The silver halide emulsion layer has different sensitivity,
For example, high sensitivity and low sensitivity silver halide emulsion layers may be separately coated. In this case, an intermediate layer may be provided between each silver halide emulsion layer.

That is, an intermediate layer made of a hydrophilic colloid may be provided if necessary. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an anti-halation layer and a backing layer may be provided between the silver halide emulsion layer and the protective layer.

In the present invention, the film surface pH on the surface on which the emulsion layer is coated must be 6.0 or more.

Here, the film surface pH in the present invention is 1 cm ²
It is the value measured by adding 0.05 cc of water onto the photographic light-sensitive material, leaving it in an atmosphere of 90% RH or more for 10 minutes, and then using a silver chloride flat electrode. A specific example of the flat electrode is a flat electrode GST-5313F manufactured by Toa Denpa Kogyo Co., Ltd.

The compound represented by formula [H] is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention.

Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described.

The silver halide may be of any composition. For example, silver chloride, silver chlorobromide, silver chloroiodobromide,
There is pure silver bromide or silver iodobromide. The average grain size of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, and particularly preferably 0.10 to 0.40 μm.

The grain size distribution of the silver halide grains used in the present invention is arbitrary, but the monodispersity value defined below is from 1 to 30.
It is preferable to adjust it so that it is in the range of 5 to 20.

Here, the monodispersity is defined as a value obtained by multiplying the standard deviation of the particle size by the average particle size by 100 times. For the sake of convenience, the grain size of silver halide grains is represented by the edge length in the case of cubic grains, and other grains (octahedral, 14
The surface area) is calculated by the square root of the projected area.

When the present invention is carried out, for example, as the grains of silver halide, those of a type having a multi-layered laminated structure of at least two layers can be used. For example, silver iodobromide in the core portion and shell portion can be used. A silver iodobromide grain having silver bromide can be used. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention are complex salts containing a cadmium salt, a zinc salt, a lead salt, a thallium salt, and an iridium salt (in the process of forming and / or growing the grain). ), A rhodium salt (complex salt containing) and an iron salt (complex salt containing), at least one metal ion is added to allow these metal elements to be contained inside and / or on the surface of the particle. It is possible to impart the reduction sensitization to the inside of the grain and / or the surface of the grain by placing in a suitable reducing atmosphere.

Further, the silver halide can be sensitized by using various chemical sensitizers in combination. Examples of the sensitizer include active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiacinate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.) ), Reduction sensitizers (triethylenetetramine, silver tin 1 tin, etc.), such as potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatiate. Nate, various precious metal sensitizers represented by sodium chloroparadite, etc.
Alternatively, two or more kinds can be used in combination.

When using a monetary sensitizer, Rhodan ammon can be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains having a surface sensitivity higher than the internal sensitivity, that is, silver halide grains giving a so-called negative image, and therefore, they should be treated with the above chemical sensitizer. Can improve the performance.

The silver halide emulsion used in the present invention includes mercaptos (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-prombenzotriazole, 5-methylbenzotriazole). ), Benzimidazoles (6-nitrobenzimidazole), indazoles (5-nitroindazole) and the like can be used for stabilization or fogging suppression. In order to increase sensitivity, increase contrast, or accelerate development, Research Disclosure 17463 may be used in the light-sensitive silver halide emulsion layer or its adjacent layer.
The compounds described in paragraphs B to D of item A can be added.

A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide emulsion used in the present invention.

When the compound of the general formula according to the present invention is added to the hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support at 10 g / m ² or less.

Examples of the support usable in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester film such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

To develop the silver halide photographic light-sensitive material of the present invention, the following developing agents are used, for example. Typical examples of HO- (CH = CH) n-OH type developing agents include hydroquinone, and catechol and pyrogallol.

As the HO- (CH = CH) n-NH ₂ type developer, ortho and para aminophenols or aminopyrazolones are typical ones, and N-methyl-p-aminophenol, N-β -Hydroxyethyl-p-aminophenol, p-
Examples include hydroxyphenylaminoacetic acid and 2-aminonaphthol.

Heterocyclic type developers include 1-phenyl-3
Examples thereof include 3-pyrazolidones such as -pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.

In addition, The James of the Photographic Process 4th Edition by The James James (The
Theory of the Photographic Process, Fourth Editio
n) Pages 291-334 and the Journal of the American Chemical Society.
Chemical Society) Vol. 73, page 3,100 (1951), 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 have a pH adjusting and buffering function with caustic alkali, alkali carbonate or amine as used in general black and white developers.

[0082]

EXAMPLES The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited to these.

Example 1 (Preparation of silver halide emulsion grains) A silver halide emulsion having a silver halide composition of 98 mol% silver bromide and 2 mol% silver iodide was used at 50 ° C., pAg 7.8 and pH 2.0. Was prepared under the following conditions. The silver ion and the haloid ion are supplied by the simultaneous mixing method,
At that time, the supply amount was increased in proportion to the surface area as the silver halide grains formed grew. Further, immediately before the completion of grain formation, 6 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver, and after completion of grain formation, partial halogen substitution was carried out using 0.3 mol of potassium iodide per mol of silver. After that, desalting is carried out by a conventional method, and the following compounds [A], [B], [C]
An ossein gelatin solution containing a mixture of was added and redispersed.

The obtained emulsion had an average grain size of 0.2 μm and a coefficient of variation.
The emulsion consisted of 10% cubic grains. After the compound represented by [X] of the present invention or the comparative compound was added as shown in Table 1, chemical sensitization was performed.

[0085]

[Chemical 19]

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

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion Silver amount
3.2 g / m ² antifoggant: 5-nitroindazole 10 mg / m ² : 1-phenyl-5-mercaptotetrazole 2 mg / m ² Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7- Tetrazaindene 30 mg / m ² hydrazine derivative (shown in Table 1) 3 × 10 ^-5 mol / m ² Surfactant: sodium dodecylbenzenesulfonate 0.1 g / m ² Sensitizing dye: anhydro-5,5'-dichloro -9-Butyl-3,3'bis (3-sulfopropyl) oxacarbocyanine hydroxysodium salt 8mg / m ²

[0088]

[Chemical 20]

Formulation (2) (Emulsion protective layer composition) Gelatin 0.9 g / m ² Matting agent: Silica having an average particle size of 3.5 μm 10 mg / m ²

[0090]

[Chemical 21]

[0091] Gelatin 2.4 g / m ² Surfactant: Sodium dodecylbenzenesulfonate ^{0.1mg / m 2 S-1:} 6.0mg / m 2 Formulation (4) (Backing protective layer composition) Gelatin 1 g / m ² Matting agent: Polymethylmethacrylate having an average particle diameter of 3.0 to 5.0 μm 50 mg / m ² Surfactant: S-2 10 mg / m ² Hardener: Glyoxal 25 mg / m ² : H-1 35 mg / m ² A quality test was conducted according to the method, and the samples were evaluated. The results are shown in Table 1.

(Black spot quality test method) Pattern exposure of halftone dots was performed with a plate making scanner SG747RU manufactured by Dainippon Screen Co., Ltd. This sample was subjected to development processing under the following conditions with an automatic developing machine for rapid processing in which a developing solution and a fixing solution having the following developing solution formulation and fixing solution formulation were introduced.

Observing the halftone dots with a magnifying glass of 100 times, the one with no black spots in the halftone dots was given the highest rank "5" and ranked according to the degree of occurrence of black spots in the halftone dots. “4”, “3”, “2”, “1” and their ranks were sequentially lowered and evaluated. In the ranks "1" and "2", black spots are large, which is a level unfavorable for practical use.

(Sensitivity test method) Also, the obtained sample is referred to as I, I
Exposure, development, and fixing were performed under the two conditions of I to determine the sensitivity. The sensitivity is the reciprocal of the exposure amount that gives a fog density + 3.0 density, and was determined as a relative value with the sensitivity of Sample No. 1 under condition I being 100.

I: The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 3 seconds, and immediately thereafter, an automatic developing machine GR-26SR (Konica (Manufactured by Co., Ltd.) under the following conditions. II: In order to see the change in sensitivity depending on the time until post-exposure processing, after exposing under the above conditions, shielded from light, 23 ℃, 60% RH
After being stored for 24 hours under the above environment, the treatment was performed under the above conditions.

<Processing Conditions> The processing conditions are as follows.

[Developer solution formulation] Sodium bisulfite 40g N-methyl-P-aminophenol sulfate 350mg Ethylenediaminetetraacetic acid disodium salt 1g Sodium chloride 5g Potassium bromide 1.2g Trisodium phosphate 75g 5-Methylbenztriazole 250mg 2 -Mercaptobenzthiazole 23 mg Benztriazole 83 mg Hydroquinone 29 g Diisopropylaminoethanol 2.3 ml Amine compound Am-1 0.5 ml Potassium hydroxide Amount to bring the pH of the working solution to 11.6.

[0098]

[Chemical formula 22]

[Fixing solution formulation] Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50% W / V) V aqueous solution) 15.7g Gluconic acid (50% W / W aqueous solution) 8.55g Aluminum sulphate (48% W / W aqueous solution) 13ml Glutaraldehyde 3g Sulfuric acid The pH of the used solution is 4.6. Add water to 1 liter when using. Finished

[Development Processing Conditions] Process Temperature Time Image 38 ° C. 30 seconds Fixing 38 ° C. 20 seconds Water washing Normal temperature 15 seconds Drying 40 ° C. 15 seconds The results are shown in Table 1.

[0101]

[Table 1]

From the results shown in Table 1, it is understood that the samples of the present invention have high sensitivity and few black spots. Further, it can be seen that the sensitivity changes little with the time from exposure to development. Example 2 The procedure of Example 1 was repeated, except that a nucleation accelerator N-10 was added to the silver halide emulsion layer in an amount of 3 × 10 ^-5 mol / m ² and the following formulation was used as a developing solution. The results are shown in Table 2.

[Developer formulation] (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 ml 1-Phenyl-5-mercaptotetrazole 30 mg Potassium bromide 4.5 g Potassium hydroxide Amount to make the pH of the used solution 10.5 (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid dipotassium salt 25 mg Acetic acid ( 90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer was used, it was dissolved in 500 ml of water to the above composition A and composition B to make 1 liter and used.

[0104]

[Table 2]

From the results shown in Table 2, as in the case of Example 1, good results were obtained with the sample of the present invention.

[0106]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity, less black spots, and sufficient chemical sensitization so that the sensitivity does not change with time after exposure.

Claims (2)

[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 said emulsion layer or other hydrophilic colloid layer, said emulsion being used. A silver halide photographic light-sensitive material characterized in that part or all of a silver halide emulsion in a layer is chemically sensitized in the presence of a polysulfide compound. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine derivative is represented by the following general formula [H]. [Chemical 1]