JPH06161010A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material which can exhibit high-contrast photographic characteristics with a stable developer, can maintain the stable photographic characteristics with the developer of low pH, makes it possible to obtain the sufficiently high max. density with the developer of low pH when applied to a silver halide photographic sensitive material of a direct positive type and makes it possible to obtain good image quality in spite of fogging development of a short period of time. CONSTITUTION:This silver halide photographic sensitive material contains at least one of the compds. expressed by formula in at least one layer of photograph constituting layers. In the formula, Y<+> denotes onium; X<-> denotes anion. L denotes an alkylene group or alkenylene group; R denotes a hydrogen atom or aliphat. group. X2 denotes a substd. group; n denotes an integer from 0 to 4. A1 and A2 are both hydrogen atoms but the one thereof is the hydrogen atom and the other denotes an acyl group, sulfonyl group or oxaryl group. G denotes a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group or iminomethylene, etc.; R1 denotes a hydrogen atom or blocking group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a novel silver halide photographic light-sensitive material having super-high contrast photographic characteristics used in a photomechanical process, and a direct image of good image quality. The present invention relates to a positive type silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In the process of converting a continuous tone density change of an original in a photolithography process into a set of halftone dots having an area proportional to the density, a silver halide photographic light-sensitive material having a high photographic property is generally used. Material is used.

Conventionally, in order to impart a high contrast property to an image, there has been disclosed in Japanese Laid-Open Patent Publication No. 56-106244 and US Pat. No. 4,686,167.
As shown in the specification, a silver halide photographic light-sensitive material contains a compound such as hydrazine as a so-called contrast-increasing agent, and further, silver halide grains capable of effectively exhibiting the contrast-increasing characteristics of the compound are used. Alternatively, other photographic additives were appropriately combined to obtain a desired photographic light-sensitive material. Such a silver halide photographic light-sensitive material is certainly stable as a light-sensitive material, and a high-contrast photographic image can be obtained even by processing with a developing solution capable of rapid processing.

However, the system using the hydrazine compound as described above generally has a drawback that it must be developed at a high pH value, and conventionally, the pH value is 1 or less.
Development was done at 1.5 or above. Such a strong alkaline developer is liable to undergo air oxidation and its developing characteristics are changed, which is inconvenient for long-term storage, and it is also problematic in terms of corrosion of the developing device, work safety and environmental problems of waste liquid. It is not preferable from the viewpoint.

With respect to avoiding the problem of a strongly alkaline developing solution, a silver halide photographic light-sensitive material capable of obtaining a high-contrast photographic image with a developing solution having a low pH value such as 11.2 or less is disclosed in European Patent No. No. 253,665, 333,435
No. 345,025, No. 356,898, U.S. Pat.No. 4,98
8,604, 4,994,365, 5,041,355 and JP-A-63-223744, 63-234244, 63-234245.
Nos. 63-234246 and 2-77057. However, the activity of the contrast-increasing agents used for these is significantly changed with the pH change of the developer at a pH of 11.2 or less, so that the pH of the developer may be affected by processing fatigue or air oxidation. Since the gamma and the sensitivity are liable to change, there is a drawback that a good halftone dot quality and a preferable black pin (sand-like or pin-like fog generated in an unexposed portion) level cannot be stably obtained.

Accordingly, there is a demand for a silver halide photographic light-sensitive material which can obtain a sufficiently high contrast even with a developer having a low pH value and has stable photographic characteristics even when the pH changes.

On the other hand, as one of the methods for forming a positive image using a direct positive type silver halide photographic light-sensitive material, an unfogged internal latent image type silver halide emulsion is used.
A method is known in which after image exposure, surface development is performed in the presence of a fogging agent to obtain a positive image.

Various techniques have been known so far in this technical field. For example, U.S. Pat.
No. 2, No. 2,456,957, No. 2,497,875, No. 2,588,98
2, British Patent No. 1,151,363, Japanese Patent Publication No. 43-29405
JP, 47-9434, 47-9677, 47-32813, the same
47-32814, 48-9727, 48-9717, U.S. Pat.Nos. 3,761,266, 3,496,577, JP-A-50-8524
No. 50-38525 and the like are the main ones.

Hydrazine compounds are known as useful fogging agents.

For example, US Pat. Nos. 2,563,785 and 2,5
88,982 hydrazine compounds, U.S. Pat.No. 2,064,700 naphthylhydrazine sulfonic acid, or British Patent 1,403,01
Sulfomethylhydrazines described in No. 8 are used as fogging agents. See also
Japanese Patent Publication No. 84 describes that a color positive image can be obtained using a hydrazide or a hydrazone compound.

However, when these compounds are used, the induction period until the start of development is long as compared with the usual development of latent image silver, and therefore the development is considerably delayed. Further, in the prior art, when applied to the use of a multilayer color photographic light-sensitive material, it is easy to cause non-uniformity of characteristics between layers,
There was a problem that the maximum density finally obtained was low.

Further, in order to maintain a preferable fog effect and obtain good results, development has been conventionally carried out under a high pH value of 12 or more, which significantly accelerates the deterioration of the developing agent. However, it is not desirable because it lowers the film physical properties of the photographic light-sensitive material. Therefore, also for the direct positive type silver halide photographic light-sensitive material, a light-sensitive material using an advantageous fogging agent that solves the above problems is desired.

[0013]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material capable of exhibiting sufficiently high contrast photographic characteristics in a stable developing solution.

A second object of the present invention is to provide a silver halide photographic light-sensitive material capable of maintaining stable photographic characteristics in a low pH developer.

A third object of the present invention is to apply it to a direct positive type silver halide photographic light-sensitive material so that a sufficiently high maximum density (Dmax) can be obtained with a developer having a low pH and fog in a short time. An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a good image quality with a large maximum density and a small minimum density (Dmin) even in the development, and having a small increase in the minimum density even after storage with time.

[0016]

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

That is, the above objects are achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following formula (I) in at least one of the photographic constituent layers. .

[0018]

[Chemical 2]

In the formula, Y ⁺ represents onium and X ⁻ represents an anion. L represents an alkylene group or an alkenylene group, and R represents a hydrogen atom or an aliphatic group. X ₂ represents a substitutable group, and n represents an integer of 0-4. A ₁ and A ₂ are
Both are hydrogen atoms, or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and R ₁ represents a hydrogen atom or a block group.

Next, the compound represented by the general formula [I] will be described in detail.

In the general formula [I], Y ⁺ represents onium,
Examples of onium include quaternary onium having a nitrogen atom or a phosphorus atom.

Among these quaternary oniums, the groups represented by the following general formulas [II], [III] or [IV] are more preferable.

[0023]

[Chemical 3]

In the formula, Z represents an atomic group necessary for forming a quaternary onium of a nitrogen-containing heterocycle.

[0025]

[Chemical 4]

In the formula, R ₂ , R ₃ and R ₄ each represent an aliphatic group, an aromatic group, an amino group or a heterocyclic group.

[0027]

[Chemical 5]

In the formula, R ₅ , R ₆ and R ₇ each represent an aliphatic group, an aromatic group or a heterocyclic group.

As the quaternary onium of the nitrogen-containing heterocycle represented by the general formula [II], a 5- or 6-membered heterocycle and these and other rings (for example, benzene, naphthalene, pyridine,
Condensed rings with thiophene, furan, pyrrole, 2H-pyrrole, etc.).

Examples of the 5-membered heterocyclic quaternary onium include oxazolium, thiazolium, selenazolium and thiazolium, and examples of the condensed ring quaternary onium of a 5-membered heterocyclic ring and another ring include benzoxazolium and Examples thereof include benzothiazolium, benzoselenazolium, naphthoxazolium and naphthothiazolium.

Examples of the 6-membered heterocyclic quaternary onium include pyridinium and pyrimidinium. As the condensed ring quaternary onium of a 6-membered heterocyclic ring and another ring, quinolinium, isoquinolinium, quinazolinium, acridinium and the like can be mentioned. Can be mentioned.

As the nitrogen-containing heterocyclic quaternary onium formed by Z, pyridinium, quinolinium, acridinium and isoquinolinium are particularly preferable.

In the general formula [III], R ₂ , R ₃ and R ₄
Are each an aliphatic group (for example, an alkyl group having 1 to 30 carbon atoms,
Alkenyl groups having 3 to 20 carbon atoms, alkynyl groups, etc., aromatic groups (eg, phenyl, naphthyl, etc.), amino groups (eg, amino, alkylamino having 1 to 20 carbon atoms), or heterocyclic groups (eg, N, A 5- or 6-membered ring containing at least one of O and S).

R ₂ , R ₃ and R ₄ are preferably aliphatic groups.

In the general formula [IV], R ₅ , R ₆ and R ₇
Are each an aliphatic group (eg methyl, ethyl, propyl, i-
Propyl, butyl, i-butyl, sec-butyl, t-butyl,
Octyl, 2-ethylhexyl, dodecyl, hexadecyl, octadecyl, cyclopropyl, cyclopentyl,
Cyclohexyl, allyl, vinyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, etc.), aromatic groups (eg phenyl, naphthyl, phenanthryl etc.) or heterocyclic groups (pyridyl, quinolyl, furyl, imidazolyl, thiazolyl, thiadiazolyl, benzotriazolyl) , Henzothiazolyl, morpholinyl, pyrimidyl, pyrrolidyl, etc.).

R ₅ , R ₆ and R ₇ are preferably aliphatic or aromatic groups.

The groups [II], [III] and [IV] above are
The above Z, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are further suitable substituents (for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic onium group,
Amino group, ammonium group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group, ureido group, alkoxy group, aryloxy group, heterocyclic oxy group, hydroxyl group, urethane group, alkylthio group,
Arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, sulfo group, carboxyl group, acyloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, nitro group, thioacyl group, thioacyl Amino group, thioureido group, etc.).

Examples of the anion represented by X ^- ₁ in the general formula [I] include halogen ion (eg, chlorine ion, bromide ion, iodide ion, etc.), carboxylate ion (eg, acetate, oxalate, fumarate, benzoate, etc.). ), Sulfonate ions (eg p-
Toluene sulfonate, methane sulfonate, trifluoromethane sulfonate, butane sulfonate, benzene sulfonate, etc.), sulfate ion, perchlorate ion, carbonate ion, nitrate ion, boron tetrafluoride ion, thiocyan ion and the like.

As the alkylene group represented by L in the formula [I], those having an alkylene group having 1 to 10 carbon atoms and a substituent (for example, an alkyl group or an aryl group) suitable for the alkylene group are preferable.

As the alkenylene group represented by L in the general formula [I], those having an alkenylene group having 2 to 10 carbon atoms and a substituent (for example, an alkyl group or an aryl group) suitable for the alkenylene group are preferable.

As L, an alkylene group is preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.

Most preferably, L in formula (I) is a methylene group.

In the general formula [I], R represents a hydrogen atom or an aliphatic group, and the aliphatic group represented by R is an alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, benzyl, etc.). , Alkenyl groups (eg, allyl, butenyl, etc.) and alkynyl groups (eg, propargyl, etc.). As R, a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is particularly preferable.

In the general formula [I], A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (eg acetyl, trifluoroacetyl, etc.), a sulfonyl group (eg methanesulfonyl, (Toluenesulfonyl, etc.) and an oxalyl group (eg, ethoxalyl, etc.).

Both A ₁ and A ₂ are preferably hydrogen atoms.

In the general formula [I], R ₁ is a hydrogen atom and an alkyl group as a blocking group (for example, methyl, ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, 4-methoxybenzenesulfonylmethyl, 1- Pyridiniomethyl, hydroxymethyl,
Methylthiomethyl, phenylthiomethyl, etc.), aryl groups (eg, phenyl, hydroxymethylphenyl, chlorophenyl, etc.), heterocyclic groups (eg, pyridyl, cenyl, furyl, etc.), —COOR ₈ , —CON (R ₉ ) (R ₁₀ Group) is preferred. R ₈ is a hydrogen atom, an alkyl group (eg methyl, ethyl, benzyl, hydroxyethyl etc.), an alkenyl group (eg allyl, butenyl etc.), an alkynyl group (eg propargyl, butynyl etc.), an aryl group (eg phenyl, naphthyl etc.). , Or a heterocyclic group (eg 2,2,6,6-
Tetramethylpiperidinyl, N-ethylpiperidinyl, tetrahydrofuryl, saturated heterocycle such as sulfolane and unsaturated heterocycle such as pyridyl, pyrimidinyl, thienyl, furyl, etc., and R ₉ and R ₁₀ are hydrogen. Atom, alkyl group (eg methyl, ethyl, benzyl, hydroxyethyl etc.), alkenyl group (eg allyl, butenyl etc.), alkynyl group (eg propargyl, butynyl etc.), aryl group (eg phenyl, naphthyl etc.), heterocyclic group (For example, 2,2,6,6-tetramethylpiperidinyl,
Saturated heterocycles such as N, N'-diethylpyrazolidinyl, quinuclidinyl, N-ethylpiperidinyl, N-benzylpiperidinyl, N-benzylpyrrolidinyl, tetrahydrofuryl, sulfolane and pyridyl, pyrimidinyl, thienyl , An unsaturated heterocycle such as furyl), a hydroxyl group, an alkoxyl group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), an alkenyloxy group (eg, allyloxy, butenyloxy, etc.), an alkynyloxy (eg, propargyloxy, butynyloxy). Etc.), aryloxy (eg phenoxy, naphthyloxy etc.), heterocyclic oxy (pyridyloxy, pyrimidinyloxy etc.) and amino group (eg amino, methylamino, dimethylamino, dibenzylamino, phenylamino etc.).

R ₁ is a hydrogen atom, a --COOR ₈ group or --CO
N (R ₉ ) (R ₁₀ ) group is preferred, and -COOR ₈ group and -CON (R ₉ ).
The (R ₁₀ ) group is more preferred.

The most preferred R ₁ in the general formula [I] includes a —COOR ₁₁ group and a —CON (R ₁₂ ) (R ₁₃ ) group (wherein R ₁₁ represents an alkynyl group or a saturated heterocyclic group). , R ₁₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₁₃ represents an alkenyl group, an alkynyl group or a saturated heterocyclic group.

In the general formula [I], the substitutable group represented by X ₂ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group (preferably having 1 carbon atom).
To an alkyl group having 20 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group (for example, phenyl, etc.), an alkoxyl group (preferably having an alkyl moiety having 1 to 20 carbon atoms), an alkenyloxy group (for example, allyloxy). , Butenyloxy etc.), alkynyloxy group (eg propargyloxy, butynyloxy etc.), aryloxy group (eg phenoxy etc.), acyloxy group (eg acetyloxy, propionyloxy, benzoyloxy etc.), acylamino group (eg acetylamino, propionylamino) , Butanoylamino, octanoylamino, benzoylamino, etc.), sulfonamide groups (eg methanesulfonamide, ethanesulfonamide, propanesulfonamide, butanesulfonamide, hexanesulfonamide, octance) Honamide, dodecanesulfonamide, benzenesulfonamide, etc.), ureido group (eg, methylureido, ethylureido, propylureido, butylureido, hexylureido, cyclohexylureido, octylureido, dodecylureido, octadecylureido, phenylureido, naphthylureido, etc.) An oxamoylamino group (for example, methyloxamoylamino, ethyloxamoylamino, butyloxamoylamino, octyloxamoylamino,
Phenyloxamoylamino etc.), hydrazinocarbonylamino groups (eg methylhydrazinocarbonylamino, ethylhydrazinocarbonylamino, dimethylhydrazinocarbonylamino, diphenylhydrazinocarbonylamino, phenylhydrazinocarbonylamino, phenylmethylhydrazinocarbonylamino) Etc.), alkylamino groups (eg methylamino, ethylamino, butylamino, octylamino, dodecylamino etc.), dialkylamino groups (eg dimethylamino, diethylamino, dibutylamino, methyloctylamino etc.), amino groups, hydroxyl groups, Halogen atom, alkylthio group (preferably having an alkyl moiety having 1 to 20 carbon atoms), alkenylthio group (eg allylthio, butenylthio, etc.), mercapto group, sulfur E group, a carboxyl group, a thioureido group (e.g., methyl thioureido, ethyl thioureido, butyl thioureido, cyclohexyl thioureido, octyl thioureido, dodecyl thioureido,
Phenylthioureido etc.), cyano group, sulfonyl group (eg methanesulfonyl etc.), sulfamoyl group (eg methylsulfamoyl, ethylsulfamoyl, butylsulfamoyl, phenylsulfamoyl etc.), carbamoyl group (eg methylcarbamoyl) , Ethylcarbamoyl, butylcarbamoyl, octylcarbamoyl, phenylcarbamoyl and the like).
These groups are further suitable groups (for example, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic onium group, amino group, ammonium group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group, Ureido group, alkoxy group, aryloxy group, heterocyclic oxy group, hydroxy group, urethane group,
Alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, sulfo group, carboxyl group, acyloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, nitro group, thioacyl group , A thioacylamino group, a thioureido group, etc.).

The compound of the general formula [I] of the present invention is preferably applied to a silver halide photographic light-sensitive material and does not substantially have a large absorbance in the visible region, and quantitatively dissolved in methanol. In this case, it is preferable that the compound does not have a maximum absorption with a molar absorption coefficient of 10,000 or more at 400 to 700 nm.

The above molar extinction coefficient is the concentration at which the absorbance at the maximum absorption wavelength of the compound at 200 to 700 nm is 1 ± 0.2 in a quartz cell having a thickness of 1 cm of the light absorption layer, using only methanol as a reference. With a methanol solution adjusted to 4,
It can be determined by measuring the absorbance at the maximum absorption wavelength at 00 to 700 nm and the concentration of the compound in a methanol solution, and applying the Lambert-Beer law.

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

[0053]

[Chemical 6]

[0054]

[Chemical 7]

[0055]

[Chemical 8]

[0056]

[Chemical 9]

[0057]

[Chemical 10]

Next, a method for synthesizing the compound represented by the general formula [I] of the present invention will be described. For example, exemplary compound I-1
Is synthesized according to the following synthetic method.

[0059]

[Chemical 11]

Exemplified compound I-14 can be synthesized according to the following synthetic method.

[0061]

[Chemical 12]

Next, a preferred embodiment of the silver halide photographic light-sensitive material of the present invention will be described when it is suitable as a light-sensitive material exhibiting high contrast photographic characteristics.

In the silver halide photographic light-sensitive material capable of obtaining a high contrast image to which the present invention is applied, at least one of the compounds represented by the above-mentioned general formula [I] is used as a substance functioning as a contrast increasing agent. The amount of the compound of general formula [I] contained in the photographic light-sensitive material is 5 × per mol of silver halide contained in the photographic light-sensitive material.
It is preferably 10 ⁻⁷ mol to 5 × 10 ⁻¹ mol.

It is particularly preferable to set it in the range of 5 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol.

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, between each silver halide emulsion layer,
You may provide the intermediate layer which consists of hydrophilic colloids. An intermediate layer may be provided between the silver halide emulsion layer and the protective layer. That is, if necessary, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer and a backing layer may be provided.

In order to incorporate the compound represented by the general formula [I] into the silver halide photographic light-sensitive material of the present invention so as to function as a contrast-increasing agent, it is preferable to incorporate it in the hydrophilic colloid layer in the light-sensitive material. Particularly preferably, it is contained in the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion 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
It is preferably adjusted to 30 and more preferably 5 to 20.

Here, the monodispersity is defined by the following formula.

[0070]

[Equation 1]

That is, the monodispersity is defined as a value obtained by multiplying the value obtained by dividing the standard deviation of the particle diameter by the average particle diameter by 100, and multiplying it by 100. The grain size of silver halide grains is represented by the edge length of cubic grains for convenience, and the 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 grains of silver halide, grains of the type having a multilayer laminated structure of at least two layers can be used. For example, the core portion is silver chloride or silver iodobromide. It is possible to use silver chlorobromide grains or silver chloroiodobromide grains in which the gel portion is silver bromide, the core portion is silver bromide, and the gel portion is silver chloride. At this time, iodine can be contained in any layer, but iodine is preferably within 5 mol%.

The silver halide grain used in the silver halide emulsion of the present invention is a complex salt 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 (containing complex salt), and an iron salt (containing complex salt), at least one metal ion may be added to contain these metal elements inside the particle and / or on the particle surface. Further, by placing in an appropriate reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside of the grain and / or the surface of the grain.

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.), such as potassium chloroaurite,
Various metal sensitizers typified by potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc. may be used alone or in combination. They can be used in combination of two or more kinds. When a gold sensitizer is used, rodan ammon can be used as an auxiliary agent.

When the present invention is applied to a light-sensitive material capable of obtaining a high-contrast image, the silver halide grain is a grain having a surface sensitivity higher than the internal sensitivity, that is, a silver halide grain giving a so-called negative image. Since it can be preferably applied to the material, the performance can be enhanced by treating with the above chemical sensitizer.

The silver halide emulsion used is a mercapto compound (1-phenyl-5-mercaptotetrazole, 2-mercapto
For example, mercaptobenzothiazole), benzotriazoles (5-bromobenzotriazole, 5-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole) or the like can be used for stabilization or fogging suppression. (Note that the silver halide emulsion used in the present invention includes a sensitizing dye, a plasticizer, an antistatic agent, a surfactant,
A hardener, a development accelerator, etc. can also be added. When the compound of the general formula [I] 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.

In the practice of the present invention, the support which can be used in the light-sensitive material for obtaining a high contrast image is, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
Examples thereof include glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material. To develop a silver halide photographic light-sensitive material that gives a high-contrast image, 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.

Further, 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, The James of the Photographic Process 4th Edition by TH James (T
he Theory of the Photographic Process, Fourth
Edition, pages 291-334 and the Journal of the American Chemical Society.
American Chemical Society, Vol. 73, p. 3,100 (195
The developer as described in 1) 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. (Hydroquinone when used alone, hydroquinone when used in combination with 1-phenyl-3-pyrazolidone, or hydroquinone and N-methyl-
A combination of p-aminophenols is preferred. The effect of the present invention is not impaired even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for development. Further, hydroxylamine or a hydrazine compound may be used as a preservative. In addition, pH adjustment and buffer function by caustic alkali, alkali carbonate, amine, etc., which are generally used in black and white developers, and inorganic development inhibitors such as bromcali and organic development inhibitors such as benzotriazole, ethylenediaminetetraacetic acid Metal ion scavengers such as, development accelerators such as methanol, ethanol, benzyl alcohol,
Addition of surfactants such as naphthol alkylaryl sulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin and glyoxal, ionic strength modifiers such as sodium sulfate. Is optional.

In the present invention, the light-sensitive silver halide emulsion layer, its adjacent layer or the developing solution used in the developer may contain an amine compound, a hydrazine compound, an onium salt compound or a polyamine for the purpose of increasing sensitivity, increasing contrast or promoting development. An alkylene oxide compound may be contained, and the performance of the present invention can be enhanced by the use of these compounds or the combined use of these compounds. Specific examples of these compounds include, for example, the nucleation promoting compound described in Japanese Patent Application No. 2-160539 and the general formula [P] R ₁ -O- (CH
Specific examples of the compound represented by ₂ CH ₂ O) _n H include those listed above.

Next, a preferred mode of using the light-sensitive material of the present invention as a direct positive type silver halide photographic light-sensitive material will be described.

In this case, the compound represented by the general formula [I] can function as a fogging agent. Hereinafter, when the compound represented by the general formula [I] is used as a fogging agent, this is referred to as "fogging agent of the present invention".

The fogging agent of the present invention contains at least one of them so as to fogging an internal latent image type silver halide emulsion which is an emulsion which directly gives a positive type image upon development after imagewise exposure. I'll do it. That is, the photographic light-sensitive material having the internal latent image type silver halide emulsion may be contained in the light-sensitive material in such a form that it can be subjected to development processing in the presence of the fogging agent of the present invention after exposure.

In a preferred embodiment, at least one of the fogging agents of the present invention is a silver halide emulsion layer or a layer adjacent thereto (for example, a silver halide photosensitive layer, an intermediate layer, a filter layer, a protective layer, an antihalation layer, etc.). It is contained in the inside.

The amount of the fogging agent used in the present invention can be varied within a wide range depending on the characteristics of the silver halide emulsion used, the type of the fogging agent and the developing conditions, but a photographic material having an internal latent image type silver halide emulsion is used. After the image exposure, the amount may be such that a fogging effect is obtained so that a positive image is obtained by developing with a surface developer. It is desirable that the amount gives a sufficient maximum density (for example, 2.0 or more) after the development processing.

[0088] The allowed to contain a fogging agent of the present invention to the silver halide emulsion, a suitable time after completion of aging, the silver halide 1 The fogging agent per mole × 10 ^-5 mol to 1 × 10 ^{- 1}
It is preferable that the amount of the compound is contained in about a molar amount.

In the practice of the present invention, silver halide developers that can be used in development processing include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylene. Diamines and the like or mixtures thereof are included. These developing agents may be contained in the emulsion in advance so that they act on the silver halide during the immersion in the high pH aqueous solution.

In the practice of the present invention, the developing composition used for the development processing of the direct positive type silver halide photographic light-sensitive material may further contain a specific antifoggant and development inhibitor. Alternatively, it is also possible to arbitrarily incorporate the respective compositions into the layer film of the silver halide photographic light-sensitive material. Commonly useful antifoggants include, for example, benzotriazoles, benzothiazoles such as 5-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, 5-methylbenzotriazole, 1-methyl-2- Heterocyclic thiones such as tetrazoline-5-thione and the like, aromatic and aliphatic mercapto compounds and the like are included.

When the present invention is directly applied to a positive type silver halide photographic light-sensitive material, the silver halide emulsion is an internal latent image type silver halide emulsion, that is, a latent image is mainly formed inside the silver halide grains. , An emulsion having silver halide grains having most of the photosensitive nuclei inside the grains. The silver halide for forming this emulsion includes any silver halide such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide. Particularly preferably, the emulsions used in this case are exposed to a light intensity scale over a defined period of time up to about 1 second on a portion of a sample coated with the emulsion on a transparent support and are substantially silver halide. The following surface developer A for developing only the surface image of particles containing no solvent
When developed at 20 ° C. for 4 minutes, another part of the same emulsion sample is similarly exposed to develop the image inside the grain. When developed at 20 ° C. for 4 minutes with the following internal developer B, It shows the maximum concentration not more than 1/5 of the maximum concentration obtained. Preferably, the maximum densities obtained with surface developer A are no greater than 1/10 of the maximum densities obtained with internal developers.

[0092] surface developer A Metol 1.5 g L-ascorbic acid 10 g NaBO 1 by addition of ₂ · 4H ₂ O 20g KBr 1g Water liters internal developer B Metol 2.0g sodium sulphite (anhydrous) 90.0 g Hydroquinone 8.0g of sodium carbonate - Water salt 52.5 g KBr 5.0 g KI 0.5 g Water added to 1 liter Also, internal latent image type silver halide emulsions include those prepared by various methods. For example, US Pat.
Conversion type silver halide emulsion described in the specification, or U.S. Patent Nos. 3,206,316 and 3,317,322,
No. 3,367,778, silver halide emulsions having internally chemically sensitized silver halide grains described in JP-B-43-29405, or U.S. Pat.Nos. 3,271,157 and 3,4.
No. 47,927, No. 3,531,291, a silver halide emulsion having silver halide grains containing a polyvalent metal ion, or a laminated structure described in JP-A No. 50-8524. And a silver halide emulsion containing silver iodide prepared by the ammonia method described in Japanese Patent Application No. 51-74062.

Further, the internal latent image type silver halide emulsion to be used preferably contains 1 mg to 10 g of a compound having an azaindene ring, a nitrogen-containing heterocyclic compound having a mercapto group, etc. per 1 mol of silver halide. Due to
More stable results with lower minimum concentrations can be given.

As the compound having an azaindene ring,
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is preferred. As the nitrogen-containing heterocyclic compound having a mercapto group, a pyrazole ring, 1,2,4-triazole ring, 1,2,3-
Triazole ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4-tetrazole ring, Pyridazine ring,
1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring, a ring in which 2 to 3 of these rings are condensed, for example, triazolotriazole ring, diazaindene ring, triazain There are den ring, tetrazaindene ring, pentazaindene ring and the like, phthalazinone ring and indazole ring, and 1-phenyl-5-mercaptotetrazole is preferable.

The silver halide photographic light-sensitive material of the present invention may be a black-and-white photographic light-sensitive material, a single color photographic material or a multi-color photographic light-sensitive material, particularly when it is applied to a positive type light-sensitive material. In the case of a full-color light-sensitive material, it is preferable to have a blue light-sensitive layer, a green light-sensitive layer and a red light-sensitive layer. In this case, a blue-sensitive silver halide emulsion layer usually containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler are used as photographic materials. Is formed.

In one preferred embodiment, a blue photosensitive layer, a green photosensitive layer and a red photosensitive layer are layered in this order from the side farther from the support, and a non-photosensitive layer is provided between the blue photosensitive layer and the green photosensitive layer. (Yellow filter layer) is provided.

As the yellow coupler, known acylacetanilide type couplers can be preferably used, and among these, benzoylacetanilide type compounds and pivaloylacetanilide type compounds are preferable.

As the magenta coupler, a 5-pyrazolone type coupler, a pyrazoloazole type coupler and an open chain acylacetanilide type coupler can be used.

As the cyan coupler, a naphthol type coupler and a phenol type coupler can also be preferably used.

Further, a non-photosensitive layer to be a photosensitive silver halide emulsion layer or a yellow filter layer as described above can be provided on a support, and an intermediate layer, a protective layer, an undercoat layer, a backcoat layer, It is possible to provide a number of various photographic constituent layers such as antihalation layers. As a coating method for these, a dip coating method, an air doctor coating method, an extrusion coating method, a slide hopper coating method, a curtain flow coating method and the like can be applied.

In the case of using a direct positive silver halide photographic light-sensitive material, the support may be, for example, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, a polypropylene film, a cellulose acetate film, a glass, a baryter which is optionally undercoated. Examples include paper and polyethylene laminated paper.

The above support may be opaque or transparent and can be selected according to the intended light-sensitive material.

Various photographic additives such as a wetting agent, a film physical property improving agent and a coating aid can be added to the silver halide emulsion of the light-sensitive material according to the purpose. As other photographic additives, gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, moldants, whitening agents, A developing speed adjusting agent, a matting agent and the like can also be used.

Further, in order to prevent fading of the dye image due to actinic rays of short wavelength, an ultraviolet absorber such as thiazolidone,
It is useful to use a benzotriazole, acrylonitrile, or benzophenone compound.

In the silver halide emulsion layer, gelatin or other gelatin derivative suitable for the purpose can be used as a protective colloid or a binder, and other hydrophilic binder may be used according to the purpose. Agent (binder)
Can be included. As the photographic light-sensitive material, it can be added to a photographic constituent layer such as an emulsion layer or an intermediate layer, a protective layer, a filter layer, and a backing layer according to the purpose. Agents, wetting agents and the like can be included.

Each constituent layer can be hardened with any appropriate hardener.

Further, an AS agent (antistain agent) can be used in the light-sensitive material.

[0108]

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. After adding 6.5 ml of 1% potassium iodide aqueous solution per mol of silver to this emulsion, modified gelatin (Japanese Patent Application No. 1-180787).
Example compound G-8) in No. 1 was added, and the mixture was washed with water and desalted in the same manner as in Example 1 of Japanese Patent Application No. 1-180787. The pAg at 40 ° C. after desalting was 8.0. Further, at the time of redispersion, a mixture of the following compounds [A], [B] and [C] was added as an antibacterial agent.

[0110]

[Chemical 13]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was used, in which the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ^2.
And an emulsion protective layer of the following formulation (2) so that the amount of gelatin is 1.0 g / m ² , and
On the other undercoat layer on the opposite side, a backing layer of the following formulation (3) was applied so that the amount of gelatin would be 2.4 g / m ^2, and then a backing of the following formulation (4) was applied. Protective layer is coated so that the amount of gelatin is 1.0g / m ² and samples 1-16
Got

Formulation (1) (silver halide emulsion layer composition)

[0113]

[Chemical 14]

[0114]

[Chemical 15]

Formulation (2) (emulsion protective layer composition)

[0116]

[Chemical 16]

Prescription (3) (backing composition)

[0118]

[Chemical 17]

Formulation (4) (composition of backing protective layer) Gelatin 1 g / m ² matting agent: polymethylmethacrylate having an average particle size of 3.0 to 5.0 μm 15 g / m ² Surfactant: S-2 10 g / m ² hardening agent : Glyoxal 25 mg / m ² : H-1 35 mg / m ^{2 The} obtained sample was subjected to a halftone dot quality test by the following method.

(Dot quality test method) A stepped wedge having a halftone dot area of 50% and a reticulated halftone screen (150 lines / inch) is partially attached, and the sample is brought into close contact with the step wedge with a xenon light source.
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 black dot in which no black pin was generated was ranked as the highest rank "5", and the degree of occurrence of black pin in the halftone dot was determined. The evaluation was performed by sequentially lowering the rank to “4”, “3”, “2”, and “1”.

The ranks "1" and "2" are levels that are not practically preferable.

Developer Formulation Hydroquinone 45.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 2-Sulfosalicylic acid 45.0 g Boric acid 25.0 g Potassium sulfite 110.0 g Ethylene diamine tetra Sodium acetate 1.0g Potassium bromide 6.0g 5-Methylbenzotriazole 0.6g n-Butyldiethanolamine 15.0g Add water 1 liter Adjust pH with sulfuric acid pH = 11.2 (Developer 1) pH = 11.0 (Development Solution 2) pH = 10.8 (Developer 3) pH = 10.5 (Developer 4) Fixer formulation (Composition A) Ammonium thiosulfate (72.5w / v% aqueous solution) 240ml Sodium sulfite 17g Sodium acetate / trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g (Composition B) Pure water (ion exchanged water) 17ml Sulfuric acid (50w / v% aqueous solution) 4.7g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1w / v% water-soluble) Solution) 26.5 g When using the fixing solution, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 liter. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

Development Processing Conditions (Process) (Temperature) (Time) Current image 40 ° C 15 seconds Fixing 35 ° C 15 seconds Water washing 30 ° C 10 seconds Drying 50 ° C 10 seconds Note that the silver halide emulsion in the formulation (1) is used. The following compounds (a), (b) and (c) were added as comparative compounds of the hydrazine derivative of the present invention added to the layer.

[0125]

[Chemical 18]

[0126]

[Table 1]

[0127]

[Table 2]

From Table 1, it can be seen that the samples according to the present invention have good overall evaluations of dot quality and black pin for comparison. Further, it can be seen from Table 2 that stable halftone dot quality and more preferable black pin level are given to the pH fluctuation of the developing solution in the relatively low pH region of pH = 10.5 to 11.2.

Example 2 (Preparation of Emulsion A) A monodisperse silver bromide emulsion was prepared in the following manner.

An aqueous solution containing ossein gelatin was controlled at 70 ° C., and an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were simultaneously added to the solution with vigorous stirring by a control double jet method to give an average particle size of 0.4. An octahedral emulsion of μm was obtained. To this emulsion were added 5 mg of sodium thiosulfate and 6 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was heated at 75 ° C. for 80 minutes for chemical ripening to obtain a silver bromide core emulsion. The core emulsion thus obtained was further added with an aqueous solution of silver nitrate and potassium bromide and sodium chloride (in molar ratio).
50:50) and added an aqueous solution containing, and grown to have an average particle size of 0.
A 7 μm octahedral monodisperse core / shell silver chlorobromide emulsion was obtained.
After washing with water and desalting, 1.3 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to each mole of silver at 60 ° C.
At 70 ° C. for chemical sensitization to obtain an internal latent image type silver halide emulsion.

(Preparation of Sample) Sample 17 was prepared by preparing a color photographic light-sensitive material having the following layer structure on a paper support laminated on both sides with polyethylene.

Sample 17 (unless otherwise specified, the amount of each compound is the coated amount as a number, unit: mg / dm ^2, provided that the emulsion is converted to silver. The structure of the compound is shown below.) 7th layer (protective layer) Gelatin 12.3 6th layer (UV absorbing layer) Gelatin 5.4 UV absorber (UV-1) 1.0 UV absorber (UV-2) 2.8 Solvent (SO-3) 1.2 5th layer (blue photosensitive layer) Emulsion A ( Sensitizing dye BD-1 included) 5.0 Gelatin 13.5 Yellow coupler (YC-1) 8.4 Image stabilizer (AO-3) 3.0 Solvent (SO-1) 5.2 Compound (d) 5 × 10 ⁻³ mol / mol Ag 4 layers (yellow filter layer) Gelatin 4.2 Yellow colloidal silver 1.0 Ultraviolet absorber (UV-1) 0.5 Ultraviolet absorber (UV-2) 1.4 Color mixing inhibitor (AS-1) 0.4 Solvent (SO-3) 0.8 Third layer (Green photosensitive layer) Emulsion A (including sensitizing dye GD-1) 2.7 Ze Chin 13.0 Magenta coupler (MC-1) 2.4 Image stabilizer (AO-1) 2.0 solvent (SO-4) 3.15 Compound (d) 5 × 10 ^-3 mol / mol Ag second layer (color mixing preventing layer) Gelatin 7.5 mixing Inhibitor (AS-1) 0.55 Solvent (SO-2) 0.72 First layer (red photosensitive layer) Emulsion A (including sensitizing dyes RD-1 and RD-2) 4.0 Gelatin 13.8 Cyan coupler (CC -1) 2.1 Cyan coupler (CC-2) 2.1 Image stabilizer (AO-3) 2.2 Solvent (SO-1) 3.3 Compound (d) 5 × 10 ⁻³ mol / mol Ag SA-1 as a coating aid , SA-2, and HA-2 as a hardening agent.

The compounds used in the above layers are shown below.

[0134]

[Chemical 19]

[0135]

[Chemical 20]

[0136]

[Chemical 21]

[0137]

[Chemical formula 22]

[0138]

[Chemical formula 23]

On the other hand, in the same manner as in Sample 17, except that the compound (d) in each layer was changed to the compound (e) and the fog agent represented by the general formula [I] of the present invention shown in Table 3, 18-24 were created.

The structures of the above compounds (d) and (e) used as comparative fog agents are shown below.

[0141]

[Chemical formula 24]

The obtained sample was exposed through an optical wedge using a sensitometer and processed in the processing steps shown below.

Processing time Temperature Color development 2 minutes 33 ° C Bleach fixing 40 seconds 33 ° C Stability 20 seconds three times 33 ° C Dry 30 seconds 60-80 ° C <Color developer-1> Diethylenetriaminepentaacetic acid 2.0g Benzyl alcohol 12.8 g Diethylene glycol 3.4 g Sodium sulfite 2.0 g Sodium bromide 0.5 g Hydroxylamine sulfate 2.6 g Sodium chloride 3.2 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 4.25 g Potassium carbonate 30.0g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Water was added to 1 liter pH 10.5 (pH was adjusted with potassium hydroxide and sulfuric acid) <Bleaching fixer formulation> Thio Ammonium sulphate (54wt%) 150ml Sodium sulfite 15g Ethylenediaminetetraacetate iron 55g (III) Ammonium ethylenediaminetetraacetate (dihydrate) 4g Glacial acetic acid 8.6 1g Water was added to 1 liter pH 5.4 (pH was adjusted with ammonia water or hydrochloric acid.) <Stabilizer>1-Hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution) 1.6ml Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Ammonia water 2.5ml Nitrilotriacetate / trisodium 1.0g 5-Chloro-2-methyl-4-isothiazylin-3-one 50mg 2-Octyl-4-isothiazolin-3-one 50mg Optical brightener (4,4 ′ -Diaminostilbene system) 1.0 g water was added to 1 liter pH 7.5 (pH was adjusted with potassium hydroxide or hydrochloric acid.) (Process-2) except that the pH of the color developer was adjusted to 11.0.
This is the same as Process-1.

Sensitometry was performed on the obtained image to evaluate the maximum density Dmax and the minimum density Dmin for the magenta image, and Table 3 shows the results.

[0145]

[Table 3]

As is clear from Table 3, the samples containing the fog agent of the present invention (Samples 19 to 24) were lower in pH treatment than the samples containing the comparative compound which is a known fog agent (17, 18). It was found that an excellent positive image having a large maximum density and a small minimum density was obtained.

Example 3 Samples 25 to 32 were prepared in exactly the same manner as in Example 2.

These samples were exposed in the same manner as in Example 2,
Processed in Process-1. The minimum density of the obtained magenta image is Dmin.

On the other hand, the raw sample (sample before exposure and development)
The sample was stored under the conditions of 50 ° C. and 80% RH for 3 days, forcibly deteriorated, and exposed and processed in the same manner as above. The minimum density of the magenta image at this time is (Dmin) '.

Table 4 shows the values of Dmin and (Dmin) '.

[0151]

[Table 4]

As is clear from Table 4, the samples containing the antifoggant of the present invention (Samples 27 to 32) have a longer storage time than the samples containing the comparative compound which is a known antifoggant (25, 26). It can be seen that the increase in the minimum concentration is small and the stability of the raw sample over time is excellent.

[0153]

EFFECTS OF THE INVENTION According to the present invention, a silver halide having a good halftone quality and having a high contrast and little fog even when processed with a low pH developer having a pH of 11.2 or less, and being stable against fluctuations in development pH. It was possible to provide a photographic light-sensitive material. Further, by directly applying the present invention to a positive silver halide photographic light-sensitive material, a sufficiently high maximum density can be obtained even when developed with a developing solution having a low pH, and the maximum density can be obtained by fog development in a relatively short time. A good positive image having a large and small minimum density was obtained, and it was possible to provide an image having a minimum increase in density even after storage with time.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material characterized in that at least one of the photographic constituent layers contains at least one compound represented by the following general formula (I). [Chemical 1] Wherein, Y ⁺ represents an onium, X ^- ₁ is an anion. L represents an alkylene group or an alkenylene group, and R represents a hydrogen atom or an aliphatic group. X ₂ represents a substitutable group, and n represents an integer of 0-4. 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. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and R ₁ represents a hydrogen atom or a block group. ]