JPH0713284A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To restrain occurrence of fog in a dot pictures and to obtain superior dot characteristics by incorporating a hydrazine compound in one of emulsion layers and other constituent layers and a specified compound in one layer. CONSTITUTION:The silver halide photographic sensitive material has at least each one silver halide emulsion layer on a support and the hydrazine compound in at least one of the emulsion layers and other constituent layers and also one of the compounds represented by the formula in which each of R1-R4 is an aliphatic group, and J1 is a divalent bonding group having >=1 alkylene oxide of repeating unit 1. J2 is a divalent bonding group including >=1 alkylen oxide group of a divalent aliphatic group or repeating unit 1. This photographic sensitive material forms a halftone image high in contrast and low in fog and superior in halftone characteristics even when it is treated with a developing solution as low as <11 in pH.

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 particle diameter of 0.2 μm, a narrow particle distribution and a uniform particle 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 exert the high contrast property of the hydrazine derivative, the hydrazine derivative had to be treated with a developer having a pH of 11 or more. p
A developer having a high pH of H11 or more is more stable than a lith-type developer in which the developing agent is easily oxidized when exposed to air, but the oxidation of the developing agent often fails to obtain a super-high contrast image. .

In order to make up for this drawback, JP-A-63-29751 and European Patents 333,435 and 345,025 disclose silver halide photographic light-sensitive materials containing a contrast-increasing agent capable of increasing the contrast even with a developer having a relatively low pH. Is disclosed.

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 is insufficient and satisfactory halftone dot performance cannot be obtained. The current situation.

On the other hand, European Patent No. 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.

[0012]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
It is an object of the present invention to provide a silver halide photographic light-sensitive material which has a high photographic property even when processed with a developing solution of less than 1, and which suppresses fogging generated in a halftone image and has good halftone performance.

[0013]

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

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 is represented by the following general formula (I ) A silver halide photographic light-sensitive material comprising at least one compound represented by

[0015]

[Chemical 2]

[Wherein R ₁ , R ₂ , R ₃ and R ₄ represent an aliphatic group, and J ₁ represents a divalent linking group containing at least one alkylene oxide group having a repeating unit of 1]. , J ₂ represents a divalent aliphatic group or a divalent linking group containing at least one alkylene oxide group whose repeating unit is 1. The present invention will be described in detail below.

In the general formula (I), the aliphatic groups represented by R ₁ , R ₂ , R ₃ and R ₄ are linear, branched or cyclic alkyl groups (eg, methyl, ethyl, propyl, isopropyl). , Butyl, cyclohexyl, octyl, dodecyl etc.), alkenyl groups (eg allyl, 2-methylallyl, butenyl etc.), alkynyl groups (eg propargyl, butynyl etc.) and the like. These are further substituted (for example, alkyl group, aryl group, alkoxy group, aryloxy group, hydroxyl group, alkylthio group, arylthio group, sulfonamide group, carbonamide group, ureido group, sulfamoyl group, carbamoyl group, amino group, alkoxy group. Carbonyl group, carboxyl group, etc.), R ₁ and R ₂ , R ₃ and R ₄ ,
Rings connected by R ₁ and J ₁ , R ₂ and J ₁ and R ₄ and J ₂ (eg piperidine, piperazine, morpholine, pyrrolidine, etc.)
May be formed. As R ₁ , R ₂ , R ₃ and R ₄ , an alkyl group is preferable.

J ₁ and J ₂ represent a divalent linking group containing at least one alkylene oxide group whose repeating unit is 1, and the alkylene oxide group is represented by a --YO-- group. , Y is an alkylene group (eg ethylene,
Propylene, trimethylene, tetramethylene, etc.). Examples of the divalent linking group represented by J ₁ and J ₂ include —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ —,
-CH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ OCH ₂ CH
_{2 -, - CH 2 CH 2} CH 2 CH 2 OCH 2 CH 2 - each group and the like such.
Examples of the divalent aliphatic group represented by J ₂ include an alkylene group (eg, groups such as ethylene, propylene, trimethylene, and tetramethylene) and an alkenylene group (eg, groups such as vinylene and propenylene). , Alkylene groups are preferred.

Next, specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0020]

[Chemical 3]

[0021]

[Chemical 4]

[0022]

[Chemical 5]

Next, synthesis examples of the compound represented by the general formula (I) are shown.

[0024]

[Chemical 6]

120 g of NaOH was dissolved in 1.2 l of distilled water, and 500 g of (1) was dissolved under cooling with ice water. The liberated oil was extracted with 1.5 l of methylene chloride, dried over MgSO ₄ , and concentrated to obtain 425 g of pale yellow oil (2). Next, 97 g of NaH (60%) is added to D
Suspend in 1.2 l of MF and warm to 50 ° C to
(3) A solution of 135 g of DMF in 150 ml was added dropwise over 2 hours, and after the addition, the reaction was continued at the same temperature for 1 hour.

After that, 425 g of (2) is heated at 45 to 60 ° C. for 5 hours.
Then, the reaction was performed at 50 ° C. for 1 hour. The reaction solution was poured into ice water, extracted with ethyl acetate, dried over MgSO ₄ , and concentrated to give a brown oil. This oil was dissolved in dilute hydrochloric acid, washed with n-hexane, the aqueous layer was made alkaline with NaOH, the released oil was extracted with ethyl acetate, dried over MgSO ₄ , and concentrated to obtain an oil which was vacuum distilled. Te (bp17
0 to 175 ° C./0.15 mmHg fraction) 185 g of the target product I-3 was obtained. The structure was confirmed by NMR and MASS.

The content of the compound represented by the general formula (I) of the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

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

Here, the compound of the general formula (I) may be contained in the same layer as the hydrazine compound or may be contained in a different layer.

As the hydrazine compound used in the present invention, those represented by the following general formula [II] are preferable.

[0031]

[Chemical 7]

In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents an acyl group, an alkyl group or an arylsulfonyl group, an alkyl group or an arylsulfinyl group, a carbamoyl group, an alkoxy group or an aryloxycarbonyl group. Represents a group, a sulfamoyl 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, It represents a sulfonyl group or an oxalyl group.

However, B, A ₂ and the nitrogen atom to which they bind are a partial structure of hydrazone.

[0034]

[Chemical 8]

May be formed.

Further, the general formula [II] will be described in detail below.

The aliphatic group represented by A preferably has 1 to 30 carbon atoms, and is particularly a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. 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, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [II] is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [II] is preferably a monocyclic ring or a condensed ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, such as a pyrrolidine ring, Examples thereof include an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring.

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)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

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 etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), aryloxy Carbonyl group (eg phenoxycarbonyl etc.), sulfamoyl group (eg dimethylsulfamoyl etc.), sulfinamoyl group (eg methyls) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group (discussed below with respect to general formula [III]), or a heterocyclic group ( For example, a pyridine ring, a pyridinium ring, etc.) is represented.

B in the general formula [II] represents A ₂ and the nitrogen atom to which they are attached.

[0044]

[Chemical 9]

May be formed.

R ₅ represents an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

Among the hydrazine compounds used in the present invention, particularly preferred are the compounds represented by the following general formula [III].

[0050]

[Chemical 10]

In the formula, R ₇ represents an aryl group or a heterocyclic group, and R ₈ represents

[0052]

[Chemical 11]

Represents

R ₉ and R ₁₀ 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, an aryloxy group, Or a heterocyclic oxy group, R ₁₁ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Alternatively, it represents a heterocyclic group. A ₁ and A ₂ are A in the general formula [II].
₁ and A ₂ each represent the same group.

The general formula [III] will be described in more detail.

The aryl group represented by R ₇ is preferably a monocyclic or condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₇ is preferably a monocyclic or condensed ring, which is a 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen. Examples thereof include a ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₇ is an aryl group, and a benzene ring is most preferred.

[0059] A ₁ and A ₂ of the general formula [II] A ₁ and A ₂
And a hydrogen atom are the most preferable.

R ₈ is

[0061]

[Chemical 12]

Wherein R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group. (Phenyl, naphthyl, etc.), heterocyclic group (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl, quinuclidinyl, N, N'-diethylpyrazolidinyl, N-benzylpyrrolidini , 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, etc.), or a heterocyclic oxy group (pyridyloxy, etc.), and R ₉ and R ₁₀ are nitrogen. A ring (piperidine, morpholine, etc.) may be formed together with the atom. R ₁₁ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocycle. Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compound represented by the general formula [II] are shown below. However, the present invention is not limited to these.

[0064]

[Chemical 13]

[0065]

[Chemical 14]

[0066]

[Chemical 15]

[0067]

[Chemical 16]

[0068]

[Chemical 17]

[0069]

[Chemical 18]

[0070]

[Chemical 19]

[0071]

[Chemical 20]

The synthesis method of the compound represented by the general formula [II] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European patent 253,665
No. 333,435, etc. can be referred to.

The content of the compound represented by the general formula [II] of the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, when the compound represented by the general formula [II] is contained in the photographic light-sensitive material, it is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

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. 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, you may provide the intermediate layer which consists of hydrophilic colloids as needed. or,
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 protective 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. For example silver chloride,
There are silver chlorobromide, silver chloroiodobromide, pure silver bromide, silver iodobromide or silver chloroiodobromide. The average diameter of the silver halide grains is 0.
The range of 05 to 0.5 μm is preferably used, but the range of 0.10 to 0.40 μm is particularly 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 the standard deviation of particle diameter by the 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 the other grains (octahedral, tetradecahedral, etc.) are calculated by the square root of the projected area.

When the present invention is carried out, for example, as the grains of silver halide, grains of the type having a multi-layered laminated structure of at least two layers can be used. For example, silver iodobromide in the core portion, shell portion 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 include a cadmium salt, a zinc salt, a lead salt, a thallium salt and an iridium salt (including a complex salt) in the process of forming and / or growing the grain. ), A rhodium salt (including a complex salt) and an iron salt (including a complex salt), at least one kind of metal ion can be added to the metal particles inside the particle and / or on the surface of the particle. Further, the reduction sensitizing nuclei can be imparted to the inside of the grain and / or the surface of the grain by placing in an appropriate reducing atmosphere.

Furthermore, the silver halide can be sensitized with various chemical sensitizers. 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, stannous chloride, etc.), potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-
Various noble metal sensitizers represented by aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite and the like can be used alone or in combination of two or more. 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 so-called negative image. Performance can be improved.

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) and the like can be used to stabilize or suppress fogging.

The photosensitive silver halide emulsion layer or its adjacent layer is provided with Research Disclousu for the purpose of increasing sensitivity, increasing contrast or promoting development.
re) Compounds described in paragraphs B to D of 17463 can be added.

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

General formula [P] R ₁₂ —O— (CH ₂ CH ₂ O) nH [wherein R ₁₂ represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n is from 10 to 200 Represents the integer. ]
As examples of specific compounds represented by the general formula [P], Japanese Patent Application No.
2-160939, pages 94 to 96, P-1 to P-17. Of these, those having a molecular weight of 1500 or more are preferable, but not limited thereto.

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 compounds of the general formulas [I] and [II] according to the present invention are added to the hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer,
Hydrophilic colloids other than gelatin can also be used.
Each of these hydrophilic binders has 10
It is preferable to apply the coating at a rate of 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) n-OH type developing agent 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 and N-β are used. -Hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

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
Examples thereof include 3-pyrazolidones such as 3-pyrazolidone.

Others, TH. James The Theory of the Photographic Process 4th Edition (The T
heory of the Photographic Process, Fourth Edition)
Pages 291-334 and Journal of the American
Chemical Society (Journal of the American Chem
The developer described in Vol. 73, p. 3,100 (1951), 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, 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. In addition, 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 capture agents such as acetic acid, methanol, ethanol,
Benzyl alcohol, development accelerators such as polyalkylene oxides, sodium alkylaryl sulfonates, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, hardeners such as glutaraldehyde, formalin, glyoxal, sodium sulfate It is optional to add an ionic strength adjusting agent or the like.

In the developer used in the present invention, alkanolamines such as diethanolamine and triethanolamine and diethylene glycol as organic solvents,
Glycols such as triethylene glycol and alkylamino alcohols such as diethylamino-1,2-propanediol and butylaminopropanol may be contained.

[0099]

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 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 obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 9.5%) having an average grain size of 0.20 μm. To this emulsion was added 6.5 ml of 1% potassium iodide aqueous solution per mol of silver, and then modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added to carry out Japanese Patent Application No. 1-180787. It was washed with water and desalted in the same manner as in Example 1. The pAg at 40 ° C after desalting was 8.0. Further, at the time of redispersion, the following compound [A] as an antibacterial agent,
The mixture of [B] and [C] was added.

[0101]

[Chemical 21]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 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 then the following formulation The emulsion protective layer of (2) is coated so that the amount of gelatin is 1.0 g / m ² , and
On the other undercoat layer on the other side, apply a backing layer of the following formulation (3) so that the amount of gelatin will be 2.4 g / m ² ,
Further, a backing protective layer having the following formulation (4) was coated thereon so that the amount of gelatin would be 1.0 g / m ² , and samples 1-29 were obtained.

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: SD-1 8.0 mg / m ² Sensitizing dye : SD-2 0.2 mg / m ² Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: Adenine 10 mg / m ² Surfactant: Saponin 0.1 g / m ² Surfactant: S-1 8.0 mg / m ² Hydrazine derivative according to the present invention [II] 30 mg / m ² Nucleation promoting compound according to the present invention [I] 100 mg / m ² Latex polymer: LX 1.0 g / M ² Polyethylene glycol (molecular weight 4000) 0.1 g / m ² Hardener: H-1 60 mg / m ² formulation (2) (Emulsion protective layer composition) Gelatin 1.0 g / m ² Surfactant: S-2 10 mg / m ² matting agent: silica having an average particle size of 3.5 μm 3 mg / m ² hardening agent: formalin 30 mg / m ² surfactant: S-3 10 mg / m ² formulation (3) (backing layer composition) D-1 30 mg / m ² D-2 75 mg / m ² D-3 30 mg / m ² Gelatin 2.4 g / m ² Surfactant: S-1 6.0 mg / m ² Surfactant: Saponin 0.1 g / m ² Formulation (4) (Backing protective layer composition) Gelatin 1 g / m ² Matting agent: Polymethylmethacrylate having an average particle size of 3.0 to 5.0 μm 15 mg / m ² Surfactant: S-2 10 mg / m ² Hardener: Glyoxal 25 mg / m ² Hardener: H-1 35 mg / M ^{2 The} compounds used in the formulations (1), (2) and (3) are shown below.

[0104]

[Chemical formula 22]

[0105]

[Chemical formula 23]

The sample thus obtained was subjected to a halftone dot quality test by the following method.

(Dot quality test method) A step-wedge is provided with a part of a reticulated screen (150 lines / inch) having a dot area of 50%.
The sample was exposed to light for 2 seconds, and the sample was developed under the following conditions with the following developing solution and the automatic developing machine for rapid processing in which the following fixing solution was added, and the halftone quality of the sample was observed with a magnifying glass of 100 times.
The one with high halftone dot quality is ranked as "5" and the following "4",
"3", "2", "1", and the rank is sequentially lowered to 5
Graded. Incidentally, the ranks "1" and "2" are levels that are not practically preferable.

The fog in the halftone dots was also evaluated in the same manner, and the one with no black pin in the halftone dot was given the highest rank "5", and the black pin occurrence in the halftone dot was determined according to the degree of occurrence. The evaluation was performed by sequentially lowering the rank to “4”, “3”, “2”, and “1”.

Incidentally, in the ranks "1" and "2", the black pin is large, which is a level unfavorable for practical use.

Developer Formulation Developer 1 Developer 2 Ethylenediaminetetraacetic acid sodium salt 1 g 1 g Sodium sulfite 60 g 60 g Trisodium phosphate (decahydrate) 75 g 75 g Hydroquinone 22.5 g 22.5 g Sodium hydroxide 8 g 8 g Sodium bromide 3 g 3 g 5 -Methylbenzotriazole 0.25g 0.25g 1-Phenyl-5-mercaptotetrazole 0.08g 0.08g Metol 0.25g 0.25g Add water 1 liter 1 liter Adjust pH with sodium hydroxide pH = 10.8 pH = 10.5 Fixer formulation (Composition A) Ammonium thiosulfate (72.5w / v% aqueous solution) 240cc. Sodium sulfite 17g Sodium acetate / trihydrate 6.5g Boric acid 6g Sodium citrate / dihydrate 2g (Composition B) Pure water (ion exchange water) 17cc. sulfate (50% w / w aqueous solution of) 4.7 g aluminum sulfate 26.5g (Al ₂ O ₃ aqueous solution in terms content of 8.1w / w%) water 500 cc. during use of the fixing solution The above composition A, was dissolved in the order of composition B, it was used to finish the liter. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Current image 4O ℃ 15 seconds Settlement 35 ℃ 15 seconds Wash 3O ℃ 10 seconds Dry 50 ℃ 10 seconds Prescription (1) The following compounds (a) and (b) were added as comparative compounds to the nucleation-accelerating compound of the present invention added to the silver halide emulsion layer.

[0112]

[Chemical formula 24]

The results of the quality test are shown in Table 1.

[0114]

[Table 1]

As is clear from Table 1, the samples according to the present invention have good halftone dot quality and black pin for comparison.

[0116]

INDUSTRIAL APPLICABILITY The silver halide photographic light-sensitive material according to the present invention has a good effect of having good contrast and little fog even when processed with a developing solution having a low pH of less than pH 11.

Claims (1)

[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 layer of said emulsion layer or other constituent layers. A silver halide photographic light-sensitive material comprising at least one compound represented by formula (I). [Chemical 1] [Wherein R ₁ , R ₂ , R ₃ and R ₄ represent an aliphatic group, J
₁ represents a divalent linking group containing at least one alkylene oxide group whose repeating unit is 1, and J ₂ represents a divalent aliphatic group or a divalent connecting group containing at least one alkylene oxide group having 1 repeating unit. Represents a linking group of. ]