JPH05158179A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photographic sensitive material high in contrast and low in fog even when it us processed with a developing solution low in pH, such as <=pH11.2, and stable against and superior in dot quality by incorporating at least one of hydrazine derivatives in a photographic constituent layer. CONSTITUTION:The photographic constituent layer contains at least one of the compounds represented by formula I in which R is a group having both of a thioether structure and a (O-Y)m structure; Y is an optionally substituted alkylene group or the like; (m) is an integer of >=2; L is an optical alkylene group; X is a divalent aliphatic or heterocyclic group; Z is a substitutable group; (n) is an integer of 0-4 and when n is >=2, each may be same or different; each of A1 and A2 is both H or one is H and the other is acyl, sulfonyl, or oxalyl; G is carbonyl or the like; and R1 is H or a 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 JP-A-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, 2,456,957, 2,497,875, 2,588,982,
British Patent No. 1,151,363, Japanese Patent Publication No. 43-29405, JP-A Nos. 47-9434, 47-9677, 47-32813, 47-328.
No. 14, No. 48-9727, No. 48-9717, U.S. Patent No. 3,76
1,266, 3,496,577, JP-A-50-8524, 5
The main publication is the 0-38525 publication.

Hydrazine compounds are known as useful fogging agents.

For example, US Pat. Nos. 2,563,785 and 2,58
Hydrazine compounds described in 8,982, naphthylhydrazine sulfonic acid described in U.S. Pat.No. 2,064,700, 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, the prior art has problems that when it is applied to the use of a multi-layer color photographic light-sensitive material, non-uniformity of characteristics is likely to occur between the layers and the finally obtained maximum density is low.

Further, in order to maintain a preferable fogging effect and obtain good results, development has been conventionally carried out under a high pH value of 12 or more, which remarkably 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 which solves the above problems is desired.

[0015]

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 to obtain a sufficiently high maximum density (Dmax) with a low pH developer and to prevent 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.

[0018]

The 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 in that at least one of the photographic constituent layers contains at least one compound represented by the following general formula [I]. It was

[0020]

[Chemical 2]

Y is an alkylene group (eg, ethylene, propylene, trimethylene, tetramethylene, etc.), an alkenylene group (eg, vinylene, propenylene, 1-butenylene, 2-butenylene, etc.), an arylene group (eg, phenylene, etc.) and suitable for these. Substituents (eg alkyl groups,
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, alkoxyl 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, A carboxyl group, an acyloxy group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a nitro group, a thioacyl group, a thioacylamino group, a thioureido group, etc.), and m represents an integer of 2 or more.

Y is preferably an alkylene group, ethylene,
Propylene and trimethylene groups are more preferred.

In the general formula [I], R is preferably a group represented by the following general formula [II] or [III].

[0024]

[Chemical 3]

The aliphatic group of R ₂ and R ₃ includes an alkyl group (eg, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, hexyl, cyclohexyl, octyl, dodecyl, octadecyl, etc.), an alkenyl group ( Examples thereof include vinyl, allyl, butenyl), alkynyl groups (eg, propargyl, butynyl, etc.) and the like.

The heterocyclic group for R ₂ and R ₃ includes N,
5 containing at least one atom selected from O, S and Se
Member ring (for example, pyrrole, imidazole, pyrazole, thiophene, furan, isothiazole, isoxazole, triazole, tetrazole, pyrazoline, oxazole, thiazole, selenazole, imidazolidine,
Pyrazolidine, imidazoline, tetrahydrofuran, sulfolane, etc.), 6-membered ring (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, piperidine, piperazine, morpholine, pyran, dithiine, etc.) heterocyclic group and condensed ring thereof with a suitable ring (For example, benzoxazole, benzothiazole, benzoselenazole, indole, indazole, benzimidazole, benzotriazole, quinoline, isoquinoline, quinoxaline,
Quinazoline, carbazole, acridine, benzothiophene, phenothiazine, phenoxazine, thianthrene, indoline, etc.) are preferable.

Examples of the aromatic group for R ₂ and R ₃ include aryl groups such as a monocyclic ring (eg phenyl) and a condensed ring (eg naphthyl).

The aliphatic group, aromatic group and heterocycle of R ₂ and R ₃ may be further substituted with a suitable substituent as described above as a suitable substituent of Y.

Examples of the divalent linking group represented by L ₁ , L ₂ and L ₃ include groups shown below, groups consisting of combinations of the groups shown below, and substituents suitable for them (for example, suitable groups for Y). Examples of such a substituent include groups having the above-mentioned groups).

[0030] _{-CH 2 -, - CH = CH} -, - C 6 H 4 -, _{pyridinediyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an alkyl group or an aryl group), - O- , -S-, -CO-, -SO ₂
-, -CH = N- In the general formula [I], the alkylene group represented by L has 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. Those are preferable.

In formula (I), the alkenylene group represented by L is preferably one 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.

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

In general formula [I], L is most preferably a methylene group or an ethylene group.

In the general formula [I], the divalent aliphatic group represented by X is an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 20 carbon atoms and a substituent suitable for these (eg, Examples of suitable substituents for Y include those having the aforementioned groups and the like.

Examples of the divalent heterocyclic group represented by X in the general formula [I] include those having a 3- to 10-membered ring containing at least one atom selected from N, O, S and Se. However, X is a 5-membered ring (for example, pyrrole, thiophene,
Furan, imidazole, oxazole, thiazole, selenazole, isoxazole, isothiazole, oxadiazole, thiadiazole, serenadiazole, triazole, pyrroline, imidazoline, pyrrolidine, imidazolidine, pyrazolidine, tetrazole, etc., 6-membered ring (for example, pyridine, Virazin, virimidine, pyridazine, triazine, piperidine, piperazine, morpholine, pyran, dithiine, etc.) and condensed rings of these with a suitable ring (for example, benzoxazole, benzothiazole,
Preferred are benzoselenazole, benzimidazole, indole, quinoline, isoquinoline, quinoxaline, quinazoline, carbazole, acridine, benzothiophene, phenoxazine, phenothiazine, thianthrene, indoline and the like.

These heterocycles may be further substituted with a suitable substituent (for example, the groups described above as suitable substituents for Y).

In the general formula [I], the substitutable group represented by Z 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, etc.) and the like. These groups may be further substituted with a suitable substituent, and examples of the suitable substituent include the above-mentioned substituents as suitable substituents for Y.

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, benzoyl etc.), a sulfonyl group (eg methane). Sulfonyl,
Represents toluenesulfonyl or the like) or an oxalyl group (eg, ethoxalyl or the like).

Both A ₁ and A ₂ are preferably hydrogen atoms.

In the general formula [I], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [I], R ₁ is a hydrogen atom and an aliphatic group as a blocking group (for example, methyl, ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, 4-methoxybenzenesulfonylmethyl, 1 -Pyridiniomethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl etc.), aromatic groups (eg phenyl, hydroxymethylphenyl, chlorophenyl etc.), heterocyclic groups (eg pyridyl, thienyl, furyl, N-methylpyridinio etc.), amino groups (Eg methylamino, dimethylamino, phenylamino etc.), alkoxyl group (eg methoxy, ethoxy, butoxy etc.), aryloxy group (eg phenoxy etc.), —CO
OR ₄ groups and —CON (R ₅ ) (R ₆ ) groups are preferred. R ₄ 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 (for example, 2,2,6,6-tetramethylpiperidinyl, N-ethylpiperidinyl, tetrahydrofuryl,
Saturated heterocycles such as sulfolane and unsaturated heterocycles such as pyridyl, pyrimidinyl, thienyl and furyl, and R ₅ and R ₆ are each a hydrogen atom or 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.), a heterocyclic group (eg 2,2,
6,6-Tetramethylpiperidinyl, N, N'-diethylpyrazolidinyl, quinuclidinyl, N-ethylpiperidinyl, N-
Saturated heterocycles such as benzylpiperidinyl, N-benzylpyrrolidinyl, tetrahydrofuryl and sulfolane and unsaturated heterocycles such as pyridyl, pyrimidinyl, thienyl and furyl), hydroxyl groups, alkoxyl groups (eg methoxy, Ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy groups (eg allyloxy,
Butenyloxy etc.), alkynyloxy groups (eg propargyloxy, butynyloxy etc.), aryloxy groups (eg phenoxy, naphthyloxy etc.), heterocyclic oxy groups (eg pyridyloxy, pyrimidyloxy etc.), amino groups (eg amino, methylamino, Dimethylamino, dibenzylamino, anilino, etc.).

The hydrogen atom as R _1, an aliphatic group, an aromatic group, -COOR ₄ group and _{-CON (R 5) (R 6} ) group is preferably -COOR ₄
Group and _{-CON (R 5) (R 6} ) group is more preferable.

In the general formula [I], the most preferable R ₁ includes a —COOR ₇ group and a —CON (R ₈ ) (R ₉ ) group.
(R ₇ represents an alkynyl group or a saturated heterocyclic group, R ₈
Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₉ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group or an alkoxyl group).

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

[0045]

[Chemical 4]

[0046]

[Chemical 5]

[0047]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

[0053]

[Chemical 12]

[0054]

[Chemical 13]

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 general formula [I] is used as a substance functioning as a contrast increasing agent. The amount of the compound of the 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.
It may be provided in layers. 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 may have any composition. 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
The range of 0.05 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 30.
It is preferable to adjust it so that it is in the range of 5 to 20.

Here, the monodispersity is defined by the following equation.

[0063]

[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 size by the average particle size by 100, and multiplying the value by 100. The grain size of silver halide grains is represented by the edge length of cubic grains for convenience, and other grains (octahedral, tetradecahedral, etc.)
Is calculated as 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 multi-layered 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 shell portion is silver chloride. At this time, iodine can be contained in any layer, but iodine is preferably within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention have 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 (complex salt containing) and an iron salt (complex salt containing), a metal ion may be added to contain these metal elements inside the particle and / or on the surface of the particle. It is possible to impart a reduction sensitizing nucleus to the inside of the grain and / or the grain surface by placing it 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.), such as potassium chloroaurite,
Various metal sensitizers typified by potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc., respectively, or 2 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 grains are grains having a surface sensitivity higher than the internal sensitivity, that is, silver halide grains 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-mentioned chemical sensitizer.

The silver halide emulsion used is a mercapto compound (1-phenyl-5-mercaptotetrazole, 2-mercapto
(Mercaptobenzthiazole), benzotriazoles (5-bromobenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole) and the like can be used for stabilization or fogging suppression (the present invention). A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener, a development accelerator and the like can be added to the silver halide emulsion used for).

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 a hydrophilic colloid other than gelatin may also be used. it can.

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 the silver halide photographic light-sensitive material capable of obtaining 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.

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.

In addition, The James of the Photographic Process, 4th edition by The James James (The
Theory of the Photographic Process, Fourth Ed
ition) pages 291-334 and the Journal of the American Chemical Society.
rican 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 as 1-phenyl).
-3-pyrazolidone or hydroquinone and N-methyl ＝ p
-Aminophenol combinations are preferred).

Even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for development, the effect of the present invention is not impaired. Further, hydroxylamine or a hydrazine compound may be used as a preservative. Others are generally made of caustic alkali, alkali carbonate or amine as used in black and white developers.
Adjusting H and having a buffer function, and inorganic development inhibitors such as bromcali and organic development inhibitors such as benzotriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, alkyl Addition of naphthol aryl sulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin and glyoxal, ionic strength modifiers such as sodium sulfate, etc. It 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 using these compounds or by using these compounds in combination. 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—
Specific examples of the compound represented by (CH 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 is capable of fogging at least one of them with an internal latent image type silver halide emulsion, which is an emulsion giving a positive image directly upon development after imagewise exposure. It should be made to exist. 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 foggants 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.). ).

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.

In order to incorporate the fogging agent of the present invention into a silver halide emulsion, at a suitable time after the completion of ripening, about 10 ^-5 to 10 ^-1 mole of the fog agent is added to 1 mole of the silver halide. It is preferable to contain it.

In the practice of the present invention, silver halide developers that can be used in the 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 developers may be incorporated 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; aromatic and aliphatic mercapto compounds and the like are included.

When the present invention is applied to a direct 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, silver chloroiodobromide and the like.

Particularly preferably, the emulsion used in this case comprises about 1 part of a sample obtained by coating the emulsion on a transparent support.
Using Surface Developer A below, which is exposed to a light intensity scale for a defined time up to seconds and develops only the surface image of the grains, substantially free of silver halide 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. Maximum obtained 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 concentration. Preferably, the maximum densities obtained with surface developer A are no greater than 1/10 of the maximum densities obtained with internal developers.

Surface developer A Metol 1.5 g L-ascorbic acid 10 g NaBO ₂ .4H ₂ O 20 g KBr 1 g Water was added 1 liter Internal developer B Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate water Salt 52.5 g KBr 5.0 g KI 0.5 g Water is added to 1 liter Further, 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 and a nitrogen-containing heterocyclic compound having a mercapto group per 1 mol of silver halide. Due to
More stable results with lower minimum concentrations can be given.

As a 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 color photographic material or a multicolor photographic light-sensitive material, particularly as a positive-working 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.

In addition to the above-mentioned non-photosensitive layer serving as a photosensitive silver halide emulsion layer or a yellow filter layer, a support, 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 thereof 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.

To the silver halide emulsion of the light-sensitive material, various photographic additives such as a wetting agent, a film physical property improving agent and a coating aid can be added according to the purpose. As other photographic additives, gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusting agents, 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, an ultraviolet absorber such as thiazolidone for preventing fading of the dye image due to short wavelength actinic rays,
It is useful to use benzotriazole, acrylonitrile, and benzophenone compounds.

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 (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.

[0105]

EXAMPLES Specific examples of the present invention will be described below, but 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.

[0107]

[Chemical 14]

(Production 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 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. Sample 1 to 33 by coating the protective layer so that the amount of gelatin is 1.0 g / m ^2.
Got

Formulation (1) (composition of silver halide emulsion layers)

[0110]

[Chemical 15]

[0111]

[Chemical 16]

Formulation (2) (emulsion protective layer composition)

[0113]

[Chemical 17]

Prescription (3) (backing composition)

[0115]

[Chemical 18]

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 g / m ² Surfactant: S-2 10 g /
m ² Hardener: 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 was partially attached with a reticulated screen (150 lines / inch) having a dot area of 50%, and the sample was adhered to 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.

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-Butylethanolamine 15.0g Add water 1 liter Adjust pH with sulfuric acid pH = 11.2 (Developer 1) pH = 11.0 (Developer 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% aqueous solution) 26.5 g fixation At the time of use of the liquid, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter and used. 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 The silver halide emulsion in the formulation (1) The following compounds (a), (b) and (c) were added as comparative compounds of the hydrazine derivative of the present invention added to the layer.

[0120]

[Chemical 19]

[0121]

[Table 1]

[0122]

[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 with vigorous stirring, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were simultaneously added to the solution by a control double jet method to give an average particle size of 0.4. A μm octahedral emulsion was obtained. To this emulsion, 5 mg of sodium thiosulfate and 6 mg of chloroauric acid (tetrahydrate) were added 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 desalting with water, to this emulsion were added 1.3 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver, and the temperature was 60 ° C.
At 70 ° C. for chemical sensitization to obtain an internal latent image type silver halide emulsion.

(Preparation of Sample) Sample 34 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 34 (unless otherwise specified, the amount of each compound is a coating amount as a number. Unit: mg / dm ^2. However, emulsion is converted to silver. Structure of compound is shown later.) 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 each of the above layers are shown below.

[0129]

[Chemical 20]

[0130]

[Chemical 21]

[0131]

[Chemical formula 22]

[0132]

[Chemical formula 23]

[0133]

[Chemical formula 24]

On the other hand, in the sample 34, the compound (d) in each layer was replaced by the compound (e) and the fogging agent represented by the general formula [I] of the present invention shown in Table 3 in the same manner as described above. Created 35-42.

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

[0136]

[Chemical 25]

[0137]

[Table 3]

As is clear from Table 3, the samples containing the antifoggant of the present invention (Samples 36 to 42) were lower in the low pH treatment than the samples containing the comparative compound which is a known antifoggant (34, 35). It was found that a good positive image having a large maximum density and a small minimum density was obtained.

Example 3 Samples 43 to 50 were prepared in the same manner as in Example 2, except that the compounds shown in Table 4 were used as the fog agent.

These samples were exposed in the same manner as in Example 3,
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)
It was stored for 3 days under the conditions of 50 ° C. and 80% RH for forced deterioration, and then 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) '.

[0143]

[Table 4]

As is clear from Table 4, the samples containing the antifoggant of the present invention (Samples 45 to 50) were more stable after storage with time than the samples containing the comparative compound which is a known antifoggant (43, 44). It can be seen that the increase of the minimum concentration is small and the stability of the raw sample over time is excellent.

[0145]

EFFECTS OF THE INVENTION According to the present invention, even when processed with a developing solution having a low pH of 11.2 or less, the contrast is high and the fog is small, and the developing pH is low.
It was possible to provide a silver halide photographic light-sensitive material having good halftone dot quality which is stable against fluctuations. 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 comprising at least one compound represented by the following general formula [I] in at least one of the photographic constituent layers. [Chemical 1]