JPH07333774A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic material which has a contrasty photographic characteristic by reducing fog even when processed by a developer with a pH of less than 11 and even after hours of preservation of a raw material and which has still better dot characteristic by reducing fog that could be generated in a dotted image. CONSTITUTION:This silver halide photographic material has at least one silver halide emulsion layer on a carrier, contains a hydrazine compound in the emulsion layer or in at least one of other constituent layers, and contains a compound that contains in its molecules at least one group containing nitrogen atom that forms an onium group through protonation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field 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 silver halide photographic light-sensitive material capable of obtaining high contrast.

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this step, a technique based on infectious development has been used as a photographic technique capable of reproducing an ultrahigh contrast image.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average grain size of 0.2 μm, a narrow grain distribution and a uniform grain shape, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion.
By treating this lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, an image with 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.
Even in continuous use, it is difficult to keep the development quality constant.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in U.S. Pat.No. 2,419,975, JP-A-51-16623 and JP-A-51-20921, JP-A-56-106244, a hydrazine derivative is contained in a silver halide light-sensitive material. is there.

According to these methods, the concentration of sulfite ion can be kept high in the developing solution, and processing can be carried out in a state where the homeostasis is enhanced. However, in these methods, in order to fully exhibit the high contrast property of the hydrazine derivative, it was necessary to perform processing with a developer having a pH of 11 or more. A developer having a high pH of 11 or more is more stable than a lith developer which is susceptible to oxidation of the developing agent when exposed to air, but oxidation of the developing agent often fails to obtain a high contrast image. In order to compensate for this drawback, JP-A-63-29751 and European Patents 333,435 and 345,0
No. 25 discloses a silver halide photographic light-sensitive material containing a contrast-increasing agent capable of increasing the contrast even in a developer having a relatively low pH.

However, when a silver halide photographic light-sensitive material containing such a contrast-increasing agent is processed with a developer having a pH of less than pH 11, the contrast becomes insufficient and satisfactory halftone dot performance cannot be obtained. The current situation.

On the other hand, European Patent 364,166 and Japanese Patent Laid-Open Nos. 62-222241, 60-140340, 62-250439 and 62-
No. 280733 and the like describe nucleation accelerators for accelerating the increase in contrast, and it is true that the addition of these compounds to the emulsion layer improves the halftone dot performance, but sand-like dots are present in the halftone dots. It has been found that a pin-shaped fog, that is, a black pin, is generated to deteriorate the quality of a halftone dot image.

Therefore, there is a demand for a light-sensitive material using an effective contrast-increasing agent and a nucleation accelerator that solves the above problems.

[0010]

The object of the present invention is to provide a pH1
Fogging is suppressed even after processing with a raw sample over time even if processed with a developing solution of less than 1, and it has hard photographic characteristics,
It is an object of the present invention to provide a silver halide photographic light-sensitive material having a better halftone dot performance by suppressing the fog generated in a halftone dot image.

[0011]

The above objects of the present invention have been achieved by a silver halide photographic light-sensitive material having the following constitution.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine compound in at least one of the emulsion layers or other constituent layers, a protonation is used. A silver halide photographic light-sensitive material containing a compound having at least one group containing a nitrogen atom to be an onium group in the molecule.

(2) The silver halide photographic light-sensitive material as described in (1), wherein the group containing a nitrogen atom to be an onium group by the above protonation is selected from amine or a nitrogen-containing saturated heterocycle.

(3) The silver halide photographic light-sensitive material described in (1), wherein the hydrazine compound is represented by the following general formula (H-II).

[0015]

[Chemical 3]

In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, or sulfamoyl. A group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group,
A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group.

(4) The silver halide photographic light-sensitive material described in (1), wherein the hydrazine compound is represented by the following general formula (HI).

[0018]

[Chemical 4]

In the formula, R ₁ represents an aryl group or a heterocyclic group, and R ₂ represents a —NR ₃ (R ₄ ) group or a —OR ₅ group. R ₃ and R ₄
Each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R ₃ and R ₄ may form a ring with a nitrogen atom. A ₁ and _{A 2} represent A _1, A ₂ group having the same meaning as in formula (H-II).

The present invention will be described in detail below.

Compound nucleation accelerators having at least one group containing a nitrogen atom which becomes an onium group by protonation of the present invention are disclosed in US Pat. No. 4,975,354, JP-A-5-127286 and JP-A-5-232616. Amine compounds containing an onium group formed by protonating the nitrogen atom of the amine compounds described in Japanese Patent Application No. 5-150457 and the like are preferable.

Further, as the compound containing an onium group by the protonation of a group containing at least one nitrogen atom, --SH group, --SC (═NH) NH ₂ group, or --S is included in the compound.
Those which do not contain a -S- group or an unsaturated heterocyclic group are preferable. More preferred are amine compounds having at least one S and one alkyleneoxy group at the same time. Specifically, the compounds described in Japanese Patent Application No. 5-150457 are preferable. At this time, a combination of an acid and an amine compound that protonate a nitrogen atom to form onium is not particularly specified. Specific examples of the compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

The method for synthesizing the nucleation accelerator is described in US Pat.
It is synthesized as follows using an amine compound synthesized by the method described in Japanese Patent Application No. 975,354 and Japanese Patent Application No. 5-150457.

Synthesis of (I-1)

[0031]

[Chemical 11]

4.58 g of the amine compound (a) was diluted with 14 ml of acetone, and a solution of 2.5 g of c.HCl diluted with 37 ml of acetone was added thereto while cooling with an ice-water bath. After stirring at room temperature for about 1 hour, the solvent was distilled off under reduced pressure and the residue was dried to obtain compound (I-1). Yield: 5.47 g (98.56% yield) Synthesis of (I-2)

[0033]

[Chemical 12]

4.34 g of the amine compound of (a) was diluted with 13 ml of acetone, and a solution of 1.14 g of concentrated sulfuric acid diluted with 4 ml of acetone was added thereto while cooling with an ice water bath. After stirring at room temperature for about 1 hour, the solvent was distilled off under reduced pressure and the residue was dried to obtain compound (I-2). Yield: 5.32 g (yield 95.8%) The content of the above amine compound of the present invention is 1 g of silver halide.
It is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻¹ mol per mol, and particularly preferably 5 × 10 ^{−6 to} 5 × 10 ⁻² mol.

When the above-mentioned amine compound is contained in the photographic light-sensitive material in the present invention, it is preferably contained in the silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion layer. The amine compound may be contained in the same layer as the hydrazine compound or may be contained in a different layer.

Examples of the hydrazine compound used in the present invention include the compounds represented by the above general formula (H-II).

In the general formula (H-II), the aliphatic group represented by A is preferably one having 1 to 30 carbon atoms, and particularly a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. is there. Examples thereof include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, and a benzyl group. These are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Sulfoxy group, sulfonamide group, ureido group, etc.).

The aromatic group represented by A in formula (H-II) is preferably a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

In the general formula (H-II), the heterocyclic group represented by A is at least nitrogen of a monocyclic ring or a condensed ring,
Sulfur, preferably a hetero ring containing one hetero atom selected from oxygen, for example, pyrrolidine ring, imidazole ring, tetrahydrofuran ring, morpholine ring, pyridine ring, pyrimidine ring, quinoline ring, thiazole ring, benzothiazole ring, thiophene ring, A franc ring etc. are mentioned.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, Substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
40), hydrazinocarbonylamide group (preferably having 1 to 40 carbon atoms), hydroxyl group, phosphoamide group (preferably having 1 to 40 carbon atoms) and the like.

In the general formula (H-II), B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl, methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl,
Benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl etc.), alkylsulfonyl group (eg methanesulfonyl, 2-chloroethanesulfonyl etc.), arylsulfonyl group (eg benzenesulfonyl group etc.), alkylsulfinyl group (eg methanesulfinyl etc.) ,
Arylsulfinyl group (benzenesulfinyl group etc.), carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.) Aryloxycarbonyl group (eg phenoxycarbonyl etc.) Sulfamoyl group (eg dimethyl Sulfamoyl etc.), sulfinamoyl group (eg methylsulfinamoyl etc.), alkoxysulfonyl group (eg methoxysulfonyl etc.), thioacyl group (eg methylthiocarbonyl etc.), thiocarbamoyl group (eg methylthiocarbamoyl etc.), oxalyl group (described later) Or a heterocyclic group (eg, pyridine ring, pyridinium ring, etc.)
Represents

In the general formula (H-II), B is
An acyl group or an oxalyl group is particularly preferable.

In the general formula (H-II), A ₁ and A ₂ are
Both are hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.),
Represents a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.) or an oxalyl group (ethoxalyl, etc.).

Among the hydrazine compounds used in the present invention, particularly preferred are the compounds represented by the above general formula (HI).

In the general formula (HI), the aryl group represented by R ₁ is preferably a monocyclic ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring, which are represented by R _1. The heterocyclic group is preferably a 5- or 6-membered unsaturated heterocycle containing one heteroatom selected from at least nitrogen, sulfur and oxygen of a monocycle or a condensed ring, for example, a pyridine ring, a quinoline ring, a pyrimidine ring, Examples thereof include a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

In formula (HI), R ₁ is preferably an aryl group, and a benzene ring is most preferred.

In the general formula (HI), A ₁ and A
₂ represents the A ₁ and A ₂ group having the same meaning as in formula (H-II), and most preferably both hydrogen atoms.

In the general formula (HI), R ₂ is -N (R ₃ ).
R ₄ group or —OR ₅ group, wherein R ₃ and R ₄ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl). Etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl, quinuclidinyl, N, N′-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy, ethoxy, etc.), alkenyloxy group (allyloxy, etc.), alkynyloxy group (propargyloxy, etc.), an aryloxy group (phenoxy) or a heterocyclic oxy group (pyridyloxy and the like), nitrogen by R ₃ and R ₄ Ring together with atoms (piperidine, morpholine) may be formed. R ₅ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.) alkenyl group (allyl, butenyl, etc.), an alkynyl group, (propargyl, butynyl, etc.),
Aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,
2,6,6-tetramethylpiperidinyl, N-methylpiperocomol, pyridyl, etc.).

Specific examples of the compound represented by formula (HI) or (H-II) are shown below. However, the present invention is not limited to these.

[0051]

[Chemical 13]

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

The method for synthesizing the compound represented by formula (HI) or (H-II) used in the present invention is described in JP-A-62-18036.
No. 1, 62-178246, 63-234245, 63-234246,
64-90439, JP-A-2-37, 2-841, 2-947,
2-120736, 2-230233, 3-125134, U.S. Patents
The methods described in 4,686,167, 4,988,604, 4,994,365, European Patents 253,665, 333,435, etc. can be referred to.

The general formula (HI) or (H-II) of the present invention
The content of the compound represented by is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻¹ mol, and particularly 5 × 10 ^{−6 to} 5 × 10 ⁻² mol per mol of silver halide. Preferably.

In the present invention, when the compound represented by the general formula (HI) or (H-II) is contained in the photographic light-sensitive material, it is adjacent to the silver halide emulsion layer or the silver halide emulsion layer. It is preferably contained in a hydrophilic colloid.

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 may be provided as a protective layer on the emulsion layer. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, an intermediate layer composed 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 antihalation layer and a backing layer may be provided between the silver halide emulsion layer and the intermediate layer.

Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described. The silver halide having any composition can be used. Examples are silver chloride, silver chlorobromide, silver chloroiodide, pure silver bromide, silver iodobromide or silver chloroiodobromide. The average diameter of the silver halide grains is
Those having a range of 0.05 to 0.5 μm are preferably used, but those having a range of 0.10 to 0.40 μm are preferable.

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 20.
% Is preferable, and more preferably 5 to 15%. Here, the monodispersity is defined as a value (%) obtained by multiplying a value (variation coefficient) obtained by dividing a standard deviation of particle diameter by an average particle diameter by 100. 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, tetradecahedral, etc.) are calculated by the square root of the projected area.

In the practice of the present invention, for example, as the silver halide grains, those of a type having a multi-layer laminated structure of at least two layers can be used. For example, silver iodobromide in the core part and shell part A grain composed of silver iodobromide grains which is 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 cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, (complex salt is formed in the step of forming and / or growing the grain. Contained), rhodium salt (including complex salt) and iron salt (including complex salt) are used to add a metal ion, and
Further, these metal elements can be contained on the grain surface, and reduction sensitization nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

Furthermore, the silver halide can be sensitized with various chemical sensitizers. As its sensitizer,
For example, active gelatin, sulfur sensitizer (sodium thiosulfate,
Allylthiocarbamide, thiourea, allylisothiacinate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.), reduction sensitizer (triethylenetetramine,
Stannous chloride, etc.), potassium chloroaurate, potassium aurithiocyanate, potassium chloroaurate,
Various noble metal sensitizers represented by 2-aurosulfobenzothiazole methyloctide, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc. may be used alone or in combination of two or more. it can. When a gold sensitizer is used, rodan 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 negative image. Performance can be improved.

The silver halide emulsion used in the present invention includes mercaptos (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole), benzotriazoles (5-bromobenzotriazole-5-methylbenzotriazole). ), Benzimidazoles (6-nitrobenzimidazole) and the like can be used to stabilize or suppress fogging.

The light-sensitive silver halide emulsion layer or its adjacent layer is a research disclosure (Research Disclousu) for the purpose of increasing the sensitivity, increasing the contrast or promoting the development.
re) 17463 compounds described in paragraphs XXI to D can be added.

Further, it is preferable to add a compound represented by the following general formula (P).

General formula (P) R ₈ -O- (CH ₂ CH ₂ O) nH In the formula, R ₈ represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n is an integer from 10 to 200. Represents

Specific compounds represented by the general formula (P) include P-1 to P-17 described in Japanese Patent Application No. 2-160939, pages 94-96. Of these, those having a molecular weight of 1500 or more are preferable, but not limited to these.

These compounds are commercially available and can be easily obtained. These compounds are preferably added in an amount of 0.01 to 4.0 mol with respect to 1 mol of silver halide.
2 to 2 mol is more preferable. Also, two or more compounds having different values of n may be included.

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 amine compound according to the present invention and the compound represented by the general formula (HI) or (H-II) are added to the hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer. A hydrophilic colloid 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.

Typical examples of the HO (CH = CH) nOH type developing agent include hydroquinone, and in addition, catechol, pyrogallol and the like.

Typical HO (CH = CH) nNH ₂ type developers are ortho- and para-aminophenols or aminopyrazolones, such as N-methyl-p-aminophenol and N-β-hydroxyethyl-p. -Aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc.

Heterocyclic type developers include 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl
Mention may be made of 3-pyrazolidones such as-3-pyrazolidone.

Others, The Theory by TH James
4th Edition of the Photographic Process
eory of the Photographic Process, Fourth Edition)
Pages 291-334 and Journal of the American
Chemical Society (Journal of the American Chemi
Cal Society) Vol. 73, 3100 (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. Moreover, you may use a hydroxylamine and a hydrazide compound as a preservative. In addition, the pH can be adjusted by a caustic alkali, an alkali carbonate, an amine or the like used in a general black-and-white developer, and a buffer function can be provided.

The developer used in the present invention is characterized in that a developer having a pH of less than 11 can be used. Further, the developer includes an inorganic development inhibitor such as bromcali and an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, and ethylenediamine 4 Metal ion promoter such as acetic acid, development accelerator such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, sodium alkylaryl sulfonate,
Natural saponins, surfactants such as sugars or alkyl ester products of the above compounds, glutaraldehyde, formalin,
It is optional to add a hardening agent such as glyoxal and an ionic strength adjusting agent such as sodium sulfate.

The developers used in the present invention include glycols such as alkanolamines such as diethanolamine and triethanolamine as organic solvents, and alkylamino alcohols such as diethylamino-1,2-propanediol and butylaminopropanol. You may contain a class.

[0083]

EXAMPLES Examples of the present invention will be described below.
The embodiments of the present invention are not limited to these.

Example 1 In a silver halide emulsion layer of a light-sensitive material, an exemplary compound represented by the general formula (HI), a nucleation accelerator and a comparative compound (the types of which are shown in Table 1 below) are used. A sample was prepared by adding in the following manner.

Thickness 10 with an undercoat layer having a thickness of 0.1 μm on both sides
On one undercoat layer of a 0 μm polyethylene terephthalate film, a silver halide emulsion layer of the following formulation (1) was applied so that the amount of gelatin was 1.5 g / m ² and the amount of silver was 3.3 g / m ^2. Further, a protective layer having the following formulation (2) was coated thereon so that the amount of gelatin would be 1.0 g / m ^2, and on the other undercoat layer on the opposite side, according to the following formulation (3). A backing layer was coated so that the amount of gelatin would be 3.5 g / m ^2, and a protective layer having the following formulation (4) was further coated thereon so that the amount of gelatin was 1 g / m ² , and samples 1 to 1 were prepared. Got 14.

Formulation 1 (Silver Halide Emulsion Layer Composition) Gelatin 1.5 g / m ² Silver chlorobromide (AgCl 60 mol%, AgBr 40 mol%, monodispersity = 12) 3.3 g / m ² antifoggant: 4 -Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.3 g / m ² Compound of the present invention or comparative compound (nucleation promoting compound or comparative compound) Table 1 Hydrazine compound Table 1 Surfactant: saponin 0.1 g / m ² latex polymer: polyethyl acrylate 1 g / m ² sensitizing dye: (a) 5 mg / m ² (b) 15 mg / m ² (c) 15 mg / m ² (d) 10 mg / m ² (e) 3 mg / m ² development regulator: nonylphenoxy polyethylene glycol 10 mg / m ² 5-methylbenzotriazole 7 mg / m ² adenine 3 mg / m ² guanine 2 mg / m ² uracil 2 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² hydroquinone 100 mg / m ² 1-phenyl-3-pyrazolidone 10 mg / m ²

[0087]

[Chemical 18]

Formulation 2 (Emulsion protective layer composition) Gelatin 1.0 g / m ² Matting agent: Polymethyl methacrylate 50 mg / m ² having an average particle size of 3.0 to 5.0 μm Surfactant: Sodium dodecylbenzenesulfonate 10 mg / m ² Charge modification Substance: C ₈ F ₁₇ COONH ₄ 10 mg / m ² Sodium chloride 100 mg / m ² Lithium chloride 30 mg / m ² Prescription stabilizer: 2-mercaptobenzimidazole sodium sulfonate 5 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / M ² Hardener: Formalin 30 g / m ² Recipe 3 (Backing layer composition) Gelatin 3.5 g / m ² Dye-1 1 g / m ² Dye-21 g / m ² Surfactant: Saponin 0.1 g / m ² Hard Membrane agent: Glyoxal 0.1 g / m ²

[0089]

[Chemical 19]

Formulation 4 (Composition of backing protective layer) Gelatin 1 g / m ² Matting agent: Polymethyl methacrylate 0.5 g / m ² having an average particle diameter of 3.0 to 5.0 μm Surfactant: Sodium p-dodecylbenzenesulfonate 10 mg / m ² C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO ^- 10 mg / m ² Development modifier: 5-nitroindazole 12 mg / m ² 5-methylbenzotriazole 20 mg / m ² 1- Phenyl-5-mercaptotetrazole 5 mg / m ² Hardener: Formalin 30 mg / m ^{2 For the} obtained samples 1 to 14 and for its historical evaluation, aluminum was conditioned at 23 ° C and 55% for 2 hours. After sealing in a vapor-deposition moisture-proof bag and leaving it at 50 ° C. for 3 days, the dot quality and black pin were evaluated by the following methods.

<< Test method for halftone dot quality >> A return halftone screen (150 lines / inch) with a halftone dot area of 50% on a step wedge
Part of the sample was attached to the sample, exposed for 5 seconds with a xenon light source, and developed under the following conditions with an automatic processor for rapid processing equipped with the following developing and fixing solutions. The quality of halftone dots was observed with a magnifying glass of 100 times, and the one with high halftone quality was ranked as "10" and the following "9", "8",
"7", "6", "5", "4", "3", "2",
It was set to 10 ranks of "1".

The fogging in the halftone dots was also evaluated in the same manner, and the one with no black pin in the halftone dots had the highest rank of "1".
“0”, and ranks “9”, “8”, “7”, “6”, “5”, depending on the degree of occurrence of black pins generated in the halftone dots.
The rank was sequentially lowered to "4", "3", "2", "1" and evaluated.

Developer formulation (composition A) Pure water (ion exchanged water) 150cc Ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 50g Potassium sulfite (55% w / v aqueous solution) 100cc Potassium carbonate 50g Hydroquinone 15g 5-Methylbenzotriazole 200mg 1 -Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to adjust the pH of the used solution to 10.4 Potassium bromide 3g (Composition B) Pure water (ion exchanged water) 3cc Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) ) 0.3cc 5-Nitroindazole 110mg 2-Mercaptobenzimidazole-5-sodium sulfonate 30mg 1-Phenyl-3-pyrazolidone 500mg When using, dissolve the above composition A and composition B in 500cc of water in this order to make 1 liter. I was there.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240cc Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium oxalate dihydrate 2g Acetic acid (90% aqueous solution) 13.6 cc (composition B) pure water (ion-exchanged water) 17 cc sulfuric acid (50% aqueous solution) 4.7 g aluminum sulfate (Al ₂ O ₃ aqueous solution in terms content of 8.1%) 26.5 g the above composition in water 500cc in use a, composition B Were melted in this order and finished to 1 liter before use. The pH of this fixer was about 4.3.

Development processing conditions (process) (temperature) (time) Current image 38 ° C. 30 seconds Fixing 28 ° C. 20 seconds Water washing 20 ° C. room temperature 20 seconds It was added to the silver halide emulsion layer in Formula (1). The following compounds (a) and (b) were used as comparative compounds for the nucleation accelerator of the present invention.

[0096]

[Chemical 20]

Table 1 shows the results of the quality test.

[0098]

[Table 1]

As is clear from the above results, the samples Nos. 7 to 14 according to the present invention were all evaluated to rank "7" or higher and showed extremely good results without fog, while comparative samples. All of Nos. 1 to 6 are rank "6" or less, and it is hard to say that they are good.

It can be seen from Table 1 that the samples according to the present invention have better halftone dot quality and black pins for comparison. Further, in the combination of the hydrazine compound described in the present invention and the nucleation accelerator each containing an onium group by protonation, it is found that the halftone dot quality and the black pin are the best even after storage with time.

[0101]

According to the present invention, fog is suppressed even after treatment with a developing solution having a pH of less than 11 even after storage of a raw sample over time.
It was possible to provide a silver halide photographic light-sensitive material which has a hard photographic property and suppresses fogging occurring in a halftone dot image and further has a better halftone dot performance.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine compound in at least one of the emulsion layers or other constituent layers, by protonation. At least one group containing a nitrogen atom to be an onium group is present in the molecule.
A silver halide photographic light-sensitive material characterized by containing a compound having two. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the group containing a nitrogen atom to be an onium group by the protonation is selected from amine and nitrogen-containing saturated heterocycles. 3. The hydrazine compound is represented by the following general formula (H
The silver halide photographic light-sensitive material according to claim 1, which is represented by -II). [Chemical 1] In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group. Group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group, A ₁ , A
Both ₂ are hydrogen atoms or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group. 4. The hydrazine compound is represented by the following general formula (H
The silver halide photographic light-sensitive material according to claim 1, which is represented by -I). [Chemical 2] In the formula, R ₁ represents an aryl group or a heterocyclic group, and R ₂ is-.
It represents a NR ₃ (R ₄ ) group or a —OR ₅ group. R ₃ and R ₄ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group,
Represents an aryloxy group or a heterocyclic oxy group, R ₅
Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R ₃ and R ₄ may form a ring with a nitrogen atom. A ₁ and A ₂ represent A _1, A ₂ group having the same meaning as in formula (H-II).