JPH07120864A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material which has a hard-contrast photographic characteristic, suppresses the fogging generated in dot images, is capable of exhibiting the high-contrast photographic characteristic and with which good dot images are obtainable even at the time of dot expanding and these characteristics are obtainable even after the raw sample preservation. CONSTITUTION:At least one kind of the compds. expressed by the formula are incorporated into the silver halide photographic sensitive material having at least one layer of silver halide emulsion layers. In the formula R1 denotes an alkyl group, alkenyl group, alkinyl group, aryl group, heterocyclic group; R2 denotes X hydrogen atom, an alkyl group, aryl group, heterocyclic group; R denotes hydrogen atom, block group; L denotes an alkylene group, alkenylene group. At least two pieces of rings are included in the part of R1-S-L. The content of the compds. of the formula is preferably 5X10<-7> to 5X10<-7>mol per mol silver halide in the photosensitive material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material containing a compound capable of functioning as a novel nucleating agent.

[0002]

2. Description of the Related Art In the process of converting a continuous tone density change of an original in a photomechanical process into a set of halftone dots having an area proportional to this density, a silver halide photographic image having a high photographic property is generally used. A photosensitive material (hereinafter, also simply referred to as "photosensitive material") is used.

In order to impart a high contrast property to an image, conventionally, as shown in JP-A-56-106244, US Pat. No. 4,686,167 and European Patent 333,435, a light-sensitive material is
A compound such as hydrazine is contained as a so-called contrast-increasing agent, and further, silver halide grains that effectively exhibit the contrast-increasing properties of this compound are used, or other photographic additives are appropriately combined to obtain a desired light-sensitive material. Was adjusted. Such a light-sensitive material is certainly stable as a light-sensitive material for plate making, and a high-contrast photographic image can be obtained by processing with a developing solution that can be processed rapidly.

However, when a continuous tone original is converted into a halftone dot image, sand-like or pin-like fog, so-called black pin, occurs in the halftone dot, impairing the quality of the halftone dot image, or stretching. In this case, there may occur a problem that the quality of the halftone image is impaired. In particular, problems often arise after storage of raw samples. Therefore, in order to solve this problem, measures such as adding various stabilizers and inhibitors having a hetero atom have been conventionally taken, but it is not always effective.

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

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

Various techniques have been known so far in this technical field. For example, US Pat.
No. 2,456,957, No. 2,497,875, No. 2,588,982, British Patent No. 1,151,363, Japanese Patent Publication No. 43-29405, Japanese Patent Laid-Open No. 47-9434.
No. 47, No. 47-9677, No. 47-32813, No. 47-32814, No. 48-
9727, 48-9717, U.S. Patents 3,761,266, 3,496,
The major ones are 577, JP-A-50-8524, and JP-A-50-38525.

Hydrazine compounds are known as useful fogging agents.

For example, US Pat. Nos. 2,563,785 and 2,588,9
Hydrazine compounds described in US Pat. No. 2,062
Naphthylhydrazine sulfonic acids described in 4,700 or sulfomethylhydrazines described in British Patent 1,403,018 are used as fogging agents. Further, Japanese Patent Publication No. 41-17184 describes that a color positive image can be obtained by using a hydrazide or 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 a multilayer color light-sensitive material, it tends to cause non-uniformity of characteristics between layers and that 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 properties of the light-sensitive material.

Further, it was never desirable in that stable performance can be obtained even after storing the raw sample.

Therefore, even for a direct positive type photosensitive material,
A light-sensitive material using an advantageous fogging agent that solves the above-mentioned problems is desired.

[0015]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to have high-contrast photographic characteristics while exhibiting high-contrast photographic characteristics and suppressing fogging occurring in halftone dot images. It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of obtaining a good halftone dot image even at the time of bleaching and having these characteristics even after storing a raw sample.

A second object of the present invention is to apply it directly to a positive type silver halide photographic light-sensitive material to obtain a sufficiently high maximum density (Dmax) even when it is developed with a developing solution having a low pH.
An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a good image having a large maximum density and a small minimum density (Dmin) even in a short-time fog development, and having a small increase in the minimum density even after storage with time.

[0017]

The above object of the present invention is to provide at least one compound represented by the following general formula (I) in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer. Achieved by containing a silver halide photographic light-sensitive material.

[0018]

[Chemical 2]

In the formula, R ₁ is an alkyl group, an alkenyl group,
It represents an alkynyl group, an aryl group or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R represents a hydrogen atom or a block group. L represents an alkylene group or an alkenylene group. However, at least two rings are included in the R ₁ -SL part. Each of these rings may be bonded with a bond and / or an aliphatic group. J ₁
And J ₂ each represent a linking group, and n represents 0 or 1.
X represents an aromatic residue or a heterocyclic residue. 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.

The general formula (I) will be described in more detail.

R ₁ is alkyl (eg methyl, ethyl, i
-Propyl, butyl, t-butyl, hexyl, octyl, t
-Octyl, decyl, dodecyl, tetradecyl, cyclohexyl, cyclohexylmethyl, benzyl etc.), alkenyl (eg allyl, 1-propenyl, 1,3-butadienyl, 2-butenyl, 2-pentenyl, cinnamyl etc.), alkynyl (eg propargyl, 2-butynyl etc.), aryl (eg phenyl, tolyl, di-i-propylphenyl, naphthyl etc.), heterocycle (eg pyridyl, furyl,
Tetrahydrofuryl, thienyl, oxazolyl, benzoxazolyl, benzothiazolyl, etc.)
These groups are further alkyl, aryl, heterocycle, alkoxy, aryloxy, hydroxyl, halogen, amino, alkylamino, arylamino, acylamino,
It may be substituted with a group such as sulfonamide or ureido.

L represents an alkylene group (eg methylene, ethylene, trimethylene, methylmethylene, ethylmethylene, butylmethylene, hexylmethylene, decylmethylene, etc.) or an alkenylene group (eg, propynylene, butenylene, etc.). These groups may be substituted with various groups such as alkyl, aryl and heterocyclic groups.

However, at least two rings are included in the R ₁ -SL portion. Examples of this ring include an aromatic ring (eg, phenyl, naphthyl, etc.), a heterocycle (eg, piperazinyl, pyrazinyl, furyl, thienyl, pyrrolyl, oxazolyl,
Thiazolyl, indolyl, etc.) and an aliphatic ring (eg, cyclohexyl, cyclopropyl, etc.). Each ring is
It may be bound by a bond and / or an aliphatic group.

R ₂ is a hydrogen atom or alkyl (eg methyl, ethyl, methoxyethyl, benzyl etc.), aryl (eg phenyl, naphthyl, methoxyphenyl etc.), heterocycle (eg pyridyl, thienyl, furyl, tetrahydrofuryl etc.) Represents each group.

R represents a hydrogen atom or a blocking group, and specific examples of the blocking group include alkyl (eg, methyl,
Ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl etc.), aryl (eg phenyl, chlorophenyl, 2-hydroxymethylphenyl etc.), heterocycle (eg pyridyl, thienyl, furyl) Etc.), —CON (R ₃ ) (R ₄ ), and —COOR ₅ groups are preferred.

R ₃ and R ₄ are each a hydrogen atom, alkyl (eg methyl, ethyl, benzyl etc.), alkenyl (eg allyl, butenyl etc.), alkynyl (eg propargyl, butynyl etc.), aryl (eg phenyl, naphthyl etc.). ), A heterocycle (eg, 2,2,6,6-tetramethylpiperidinyl, N-ethyl-N′-ethylpyrazolidinyl,
Pyridyl, etc.), hydroxyl, alkoxy (eg, methoxy, ethoxy, etc.), amino (eg, amino, methylamino, etc.), and forms a ring (eg, piperidino, morpholino, etc.) with R ₃ and R ₄ together with a nitrogen atom. May be. R ₅ is a hydrogen atom, alkyl (eg methyl, ethyl, hydroxyethyl etc.), alkenyl (eg allyl, butenyl etc.), alkynyl (eg propargyl,
Butynyl etc.), aryl (eg phenyl, naphthyl etc.) and heterocycle (eg 2,2,6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl etc.) groups.

J ₁ and J ₂ represent a linking group, and examples of J ₁ include the following groups.

[0028] _{-CO -, - SO 2 -,} - N (A 3) CO -, - N (A 3) N
_{(A 4) CO -, -} CON (A 3) N (A 4) CO- wherein A _3, A ₄ each represents a hydrogen atom, an alkyl group, but an aryl group or a heterocyclic group, preferably n = 1 in which J ₁ is a carbonyl group.

J ₂ is specifically acylamino (eg benzoylamino, phenoxyacetylamino etc.), sulfonamide (eg benzenesulfonamide, furansulfonamide etc.), ureido (eg ureido, phenylureido etc.), alkylamino (eg Benzylamino, furfurylamino etc.), anilino, alkylideneamino (eg benzylideneamino), aryloxy (eg phenoxy), aminocarbonylalkoxy (eg aminocarbonylmethoxy), sulfonylhydrazinocarbonylamino (eg benzenesulfonylhydrazinocarbonylamino) Groups such as J ₂ is preferably a benzenesulfonamide group.

X is an aromatic residue (eg, phenylene, naphthylene, etc., or those having a substituent group), or a heterocyclic residue (eg, pyridine, pyrazole, pyrrole, etc.).
A divalent residue such as thiophene, benzothiophene, furan or the like, or those having a substituent on them.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is acyl (eg acetyl, trifluoroacetyl etc.), sulfonyl (eg methanesulfonyl,
It represents a group selected from each group of toluenesulfonyl etc.) and oxalyl (eg ethoxalyl etc.). Both A ₁ and A ₂ are preferably hydrogen atoms.

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

[0033]

[Chemical 3]

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[Chemical 25]

[0056]

[Chemical formula 26]

[0057]

[Chemical 27]

[0058]

[Chemical 28]

[0059]

[Chemical 29]

[0060]

[Chemical 30]

[0061]

[Chemical 31]

Next, a method for synthesizing the compound of the present invention will be described.

The compounds of the present invention are disclosed in JP-A-3-259240 and JP-A-3-259240.
It can be synthesized according to the method described in 45762, US Pat. No. 4,988,604 and the like.

(Synthesis of Compound I-37)

[0065]

[Chemical 32]

After 1.63 g of the compound (a) was dissolved in 9 cc of dimethylformamide, sodium hydride was gradually added. Then, the reaction vessel was immersed in an ice bath to adjust the internal temperature to 5 ° C., and (b) 4.18 g of dimethylformamide (21 cc) dissolved therein was added dropwise over 30 minutes.

After reacting at room temperature for further 5 hours, the mixture was poured into water and the solid matter was filtered and purified by column to obtain 0.95 g (yield 18%) of the desired milky white solid. The structure of the compound is NMR,
Confirmed from MS.

Compound I-37 can also be synthesized by the following route.

[0069]

[Chemical 33]

(Synthesis of Compound I-112)

[0071]

[Chemical 34]

After 7.6 g of compound Ia was dissolved in 50 cc of methanol, 4.5 g of compound Ib was gradually added at room temperature. After stirring for 30 minutes, methanol was distilled off under reduced pressure to obtain the desired product.
12.1 g was obtained. The structure of the compound was confirmed by NMR and MS.

Compound 1-112 can also be synthesized by the following route.

[0074]

[Chemical 35]

It is considered that the hydrazine compound of the present invention exerts the contrast increasing action by the mechanism shown in the following scheme.

[0076]

[Chemical 36]

Exemplified Compound I-50 was prepared by
During the development processing, first, cross-oxidation is carried out with the imagewise developed oxidant of the developing agent to obtain an azo compound such as (A). Next, (A) is hydrolyzed by the alkali in the developing solution to produce (B) and (C), but (B) is a nucleating active species, which acts on silver halide to increase the contrast. Indicates.

It is considered that the other hydrazine compounds in the present invention also exert a contrast increasing action by the same mechanism.

Next, description will be given of a preferable mode in which the light-sensitive material of the present invention is applied to a light-sensitive material exhibiting high contrast photographic characteristics.

The light-sensitive material to which a high-contrast image according to the present invention can be obtained contains at least one compound represented by the general formula (I) as a contrast-increasing agent. The amount of the compound of formula (I) contained in the material is 5 × 10 ⁻⁷ per mol of silver halide in the light-sensitive material.
It is preferably ˜5 × 10 ⁻¹ mol. Especially 5 × 10 ^-6 ~
5 × 10 ^-2 mol is preferred.

The 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 layer may be provided on each side of the support. The silver halide emulsion can be coated directly on the support or can be coated through another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the silver emulsion layer. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer composed of a hydrophilic colloid may be provided between each silver halide emulsion layer. Further, 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 for the compound represented by formula (I) to function as a contrast increasing agent, it is preferably contained in the hydrophilic colloid layer in the light-sensitive material, particularly preferably the silver halide emulsion layer and / or It may be incorporated in a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

Next, the silver halide used in the 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 chloroiodobromide, pure silver bromide, silver iodobromide or silver chloroiodobromide. The average grain size of the silver halide is preferably in the range of 0.05 to 0.5 μm, among which 0.10 to 0.40.
The one with μm is preferable.

The grain size distribution of the silver halide grains used in the present invention is arbitrary, but the monodispersity value is preferably from 1 to 30, and more preferably from 5 to 20.

Here, the monodispersity is defined by the following equation.

Monodispersity = (standard deviation of grain size) / (average grain size) × 100 Note that the grain size of silver halide grains is represented by the edge length of cubic grains for the sake of convenience and other grains ( Octahedral, 14-sided, etc.) is calculated by the square root of the projected area.

When the present invention is carried out, for example, as the grains of silver halide, those of a type having a multilayer laminated structure of at least two layers can be used, and 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 shell 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 grain used is a cadmium salt during the grain forming process and / or growing process.
A metal ion is added by using at least one selected from zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (including complex salt), and inside the particle. And / or the surface of the grain can be made to contain these metal elements, and by placing in a suitable 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 the sensitizer, for example, active gelatin, sulfur sensitizer (sodium thiosulfate,
Allylthiocarbamide, thiourea, allyl isocyanate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.), reduction sensitizer (triethylenetetramine, stannous chloride, etc.), for example potassium chloro Various precious metal sensitizers represented by aurite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc., respectively. Alone or 2
They can be used in combination of two or more kinds. When a gold sensitizer is used, rhodan ammonium can be used as an auxiliary agent.

When the present invention is applied to a light-sensitive material for high-contrast images, it is preferably applied to a light-sensitive material in which the silver halide grains are particles having a surface sensitivity higher than the internal sensitivity, so-called silver halide grains giving a negative image. Therefore, the performance can be enhanced by treating with the chemical sensitizer.

The silver halide emulsion used is a mercapto (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.

The silver halide emulsion used in the present invention can be used as a accelerating agent (nucleating accelerating agent) for nucleation infectious development.
53-77616, 54-37732, 53-137133, 60-1403
No. 40, No. 60-14959, JP-A-2-97937, U.S. Pat.
The compounds disclosed in No. 8,604, amine compounds having a ballast group or adsorption promoting group, and alcohol compounds such as diphenylcarbinol can be added.

The amount of the nucleation accelerator is preferably 2 × 10 ^-5 to 2 × 10 ^-1 mol, and particularly 1 × 10 ^-4 to 1 per 1 mol of silver halide contained in the light-sensitive material. The range of × 10 ^-2 mol is preferable.

Specific examples of the nucleation accelerator are shown below, but the invention is not limited thereto.

[0095]

[Chemical 37]

[0096]

[Chemical 38]

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

Examples of the support that can be used in the light-sensitive material of the present invention include polyester films represented by baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyethylene terephthalate. it can.
These supports are appropriately selected depending on the purpose of use of the light-sensitive material.

To develop a light-sensitive material capable of obtaining a high-contrast image, the following developing agents are used, for example.

A typical example of the HO (CH = CH) nOH type developing agent is hydroquinone, and catechol,
There is pyrogallol.

Further, as the HO (CH = CH) nNH ₂ type developing agent,
Ortho and para aminophenols or aminopyrazolones are typical, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc. There is.

As the heterocyclic type developer, 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-3
And 3-pyrazolidones such as pyrazolidone.

Others, TH. James The Theory of the Photographic Process 4th Edition (The
Theory of the Photographic Process, Fourth Editio
n) Pages 291 to 334 and the Journal of the American Chemical Society.
The developer described in Vol. 73, p. 3100 (1951) can be effectively used. 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 alone, hydroquinone and 1-in combination
Phenyl-3-pyrazolidone or hydroquinone and N-
A combination of methyl-p-aminophenol is preferred.

Even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for the development, the effect of the present invention is not impaired. Further, a hydroxylamine or a hydrazine compound may be used as a preservative. In addition, it should have a pH adjusting and buffering function with caustic alkali, alkali carbonate or amine as used in general black and white developers.
And inorganic development inhibitors such as potassium bromide and organic development inhibitors such as benzotriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxides, sodium alkylaryl sulfonates It is optional to add a surface active agent such as natural saponin, saccharide or alkyl ester of the above compound, a hardening agent such as glutaraldehyde, formalin and glyoxal, and an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention may contain alkanolamines and glycols as organic solvents.

Next, a preferred mode in which the light-sensitive material of the present invention is directly used as a positive-working 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 the "fogging agent of the present invention".

The fogging agent of the present invention may be present in such a manner that at least one of them is directly exposed to a positive type internal latent image type silver halide emulsion at the time of development processing after imagewise exposure. That is, the light-sensitive material having an 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 fog 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.). ).

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 development 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. Preferably.

The silver halide developing agents that can be used in the present invention include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines and the like or mixtures thereof. Is included. These developers 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.

The developing composition used for the development processing of the direct positive type light-sensitive material may further contain a specific antifoggant and development inhibitor. Alternatively, those compositions can be optionally incorporated into the layer film of the light-sensitive material. Commonly useful antifoggants include, for example, benzotriazoles, benzothiazoles such as 5-methylbenzothiazole; 1-phenyl-5-mercaptotetrazole, 5-methylbenzotriazole, 1-methyl-2-tetrazoline Heterocyclic thiones such as -5-thione; aromatic and aliphatic mercapto compounds and the like are included.

When the present invention is directly applied to a positive-working 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, and An emulsion having silver halide grains having most of them inside the grains. The silver halide for forming this emulsion includes any silver halide such as silver bromide,
It includes 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.
The surface developing solution A described below is used to develop only the surface image of the grain, which is exposed to the light intensity scale for a certain period of time up to 20 seconds and contains substantially no silver halide solvent.
When developed at 4 ° C for 4 minutes, another part of the same emulsion sample is similarly exposed to develop the image inside the grain. Maximum density obtained when developed at 20 ° C for 4 minutes with the following internal developer B. The maximum density is not more than 1/5. Preferably, the maximum density obtained using surface developer A is
It is not more than 1/10 of the maximum density obtained with the internal developer.

Surface developer A Metol 2.5 g L-ascorbic acid 10 g Sodium metaborate (tetrahydrate) 20 g Potassium bromide 1 g Water added 1 liter Internal developer B Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water 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 emulsions described in U.S. Pat. No. 3,206,316, U.S. Pat. No. 3,206,316, U.S. Pat. US Patent 3,271,157
No. 3,447,927, and No. 3,531,291, and silver halide emulsions having silver halide grains containing a polyvalent metal ion; halogen comprising grains having a laminated structure described in JP-A No. 50-8524. Silver halide emulsions include silver halide emulsions containing silver iodide prepared by the ammonia method described in JP-A-52-156614.

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. Can give more stable results with lower minimum concentrations.

Compounds having an azaindene ring include 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is preferred. As the nitrogen-containing heterocyclic compound having a mercapto group, pyrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,2,3-thiadiazole,
1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,2,3,
4-tetrazole, pyridazine, 1,2,3-triazine, 1,2,
4-triazine, 1,3,5-triazine, these rings are 2-3
Individually condensed rings, for example, triazolotriazole, diazaindene, triazaindene, tetrazaindene, pentazaindene, etc., phthalazinone, indazole, etc., but 1-phenyl-5-mercaptotetrazole is preferable.

The light-sensitive material of the present invention, particularly those applied to the positive-type light-sensitive material, may be a black-and-white light-sensitive material, a monochromatic color light-sensitive material or a multicolor 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 light-sensitive material is usually formed from a blue light-sensitive silver halide emulsion layer containing a yellow coupler, a green light-sensitive silver halide emulsion layer containing a magenta coupler, and a red light-sensitive silver halide emulsion layer containing a cyan coupler. To be done.

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 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 acylacetonitrile type coupler can be used.

As the cyan coupler, a naphthol type coupler and a phenol type coupler can 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 the 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 light-sensitive material, the support may be, for example, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, a polypropylene film, which is optionally undercoated.
Cellulose acetate film, glass, baryta paper,
Examples include polyethylene laminated paper.

The 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, an ultraviolet absorber such as thiazolidone for preventing fading of the dye image due to short wavelength actinic rays,
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 (binder), and other hydrophilic binder may be used according to the purpose. Agents can be included. As the light-sensitive material, an emulsion layer or an intermediate layer,
It can be added to a photographic constituent layer such as a protective layer, a filter layer and a backing layer according to the purpose, and the hydrophilic binder can contain a plasticizer and a wetting agent which are applicable according to the purpose.

Further, each constituent layer can be cured with any appropriate hardener.

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

[0133]

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

Example 1 In a silver halide emulsion layer of a light-sensitive material, an exemplary compound represented by the general formula (I) and a comparative compound (C-1 to C-shown below) were used.
3) was added in the following manner to prepare a sample.

[0135] A thickness of 10 μm with an undercoat layer having a thickness of 0.1 μm on both sides.
On one undercoat layer of a 0 μm polyethylene terephthalate film, a silver halide emulsion layer of the following formulation (1) was applied so that the amount of gelatin was 1.5 g / m ² and the amount of silver was 3.3 g / m ^2. Further, a protective layer having the following formulation (2) was coated thereon so that the amount of gelatin would be 1.0 g / m ^2, and on the other undercoat layer on the opposite side, according to the following formulation (3). A backing layer was coated so that the amount of gelatin would be 3.5 g / m ^2, and a protective layer having the following formulation (4) was further coated thereon so that the amount of gelatin was 1 g / m ² , and samples 1 to 1 were prepared. Got 16.

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

[0137]

[Chemical Formula 39]

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

[0139]

[Chemical 40]

Formulation 4 (Composition of backing protective layer) Gelatin 1 g / m ² Matting agent: Polymethylmethacrylate 0.5 g / m ² having an average particle size of 3.0 to 5.0 μm Surfactant: Sodium p-dodecylbenzenesulfonate 10 mg / m ² C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO ^- 10 mg / m ² Development modifier: 5-nitroindazole 12 mg / m ² 5-methylbenzotriazole 20 mg / m ² 1- Phenyl-5-mercaptotetrazole 5 mg / m ² Hardener: Formalin 30 mg / m ^{2 The} obtained sample was subjected to a halftone dot quality test by the following method.

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

The fog in the halftone dots is also evaluated in the same manner, and the black dots in the halftone dots having no black pin are ranked as the highest rank "5" according to the degree of occurrence of the black pins in the halftone dots. Then, the rank was evaluated by sequentially lowering the rank to "4", "3", "2", "1".

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

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

[0145] The following compounds (C-1) to (C-3) were used as comparative compounds added to the silver halide emulsion layer in the formulation (1).

[0146]

[Chemical 41]

Table 1 shows the results of the halftone dot quality test.

[0148]

[Table 1]

As is clear from the above results, with respect to the halftone dot quality, Samples 1 to 13 according to the present invention are all rank "4" or higher, but Comparative Samples 14 to 16 are rank "3". Indicates that the halftone dot quality is not good.

Also, regarding the occurrence of black pins as an index of fog, all the samples according to the present invention were evaluated to rank "5" or "4", and showed very good results without fog. On the other hand, all the comparative samples had a bad rank of "2".

Example 2 In Samples 4 and 10 of Example 1, Samples 17 to 26 were prepared by changing the monodispersity of silver halide grains to 4 to 40, and the same experiment was conducted.

When the particles were prepared, 8 × 10 ⁻⁷ mol / Agl mol of rhodium and 3 × 10 ⁻⁷ mol / Agl mol of iridium were added according to a conventional method. The silver halide composition is silver chloride
With 98 mol% of silver chlorobromide, a desensitizing dye (f) having the following structure was added instead of adding the sensitizing dyes (a) to (e).

Further, 50 mg / m ² of the following filter dye-3 was added to the protective layer, and the following ultraviolet absorbing dye-4 was added.
100 mg / m ^{2 was} added.

[0154]

[Chemical 42]

Others were the same as those in Samples 4 and 10, and the same exemplified compounds I-37 and I-50 were used as the compounds represented by the general formula (I). The monodispersity was adjusted by a conventional control double jet method by changing the pH potential at the time of charging particles and the supply amounts of Ag ions and halide ions.

Exposure and development were also carried out in substantially the same manner as in Example 1 to evaluate photographic performance. However, in this example, an ultrahigh pressure mercury lamp was used for exposing the prepared sample, and irradiation was performed with an energy of 5 mJ.

The evaluation results are shown in Table 2. Samples 17-26 are
It was found that the halftone dot qualities of 4.5 to 5 and the black pins 4.5 to 5 were all good, the halftone dot quality was high, and the fog was extremely small.

[0158]

[Table 2]

Example 3 (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 by a control double jet method under vigorous stirring to give an octahedral emulsion having an average particle size of 0.4 μm. 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. To this core emulsion, an aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio of 50:50) were added and grown to grow an octahedral monodisperse core / shell chlorobromide having an average particle size of 0.7 μm. A silver emulsion was obtained. After washing with water and desalting, 1.3 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver were added to this emulsion, and the mixture was heated at 60 ° C for 70 minutes to carry out chemical sensitization treatment and internal latent image. A type silver halide emulsion was obtained.

(Preparation of Sample) A multi-layer color light-sensitive material having the following layer structure was prepared on a paper support laminated on both sides with polyethylene to obtain Sample 27. Unless otherwise specified, the amount of each compound is indicated by a numerical value of the coating amount (unit: mg / d
m ² ). However, the values of silver equivalents of emulsions and the structures of compounds are 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 light-sensitive layer) Emulsion A (including sensitizing dye BD-1) 5.0 Gelatin 13.5 Yellow coupler (YC-1) 8.4 Image stabilizer (AO-3) 3.0 Solvent (SO-1)
5.2 Compound (C-1) 5
× 10 ^-3 mol / mol Ag 4th layer (yellow filter layer) Gelatin 4.2 Yellow colloidal silver 1.0 UV absorber (UV-1) 0.5 UV absorber (UV-2) 1.4 Anti-color mixing agent (AS-1) 0.4 Solvent (SO-3) 0.8 Third layer (green photosensitive layer) Emulsion A (including sensitizing dye GD-1) 2.7 Gelatin 13.0 Magenta coupler (MC-1) 2.4 Image stabilizer (AO-1) 2.0 Solvent (SO- 4) 3.15 Compound (C-1) 5 × 10 ⁻³ mol / mol Ag Second layer (color mixing prevention layer) Gelatin 7.5 Color mixing inhibitor (AS-1) 0.55 Solvent (SO-2) 0.72 First layer (red sensitization) 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 (C-1) 5 × 10 -3 mol / mol Ag Incidentally, the coating aid With SA-1, SA-2 Te, also,
Coating was performed using HA-1 as a hardener.

SO-1: dibutyl phthalate SO-2: dioctyl phthalate SO-3: di (3-methyl-5,5-dimethylpentyl) phthalate SO-4: di-i-decyl phthalate AS-1: di-t -Octylhydroquinone SA-1: Di (2-ethylhexyl) sulfosuccinate / sodium salt SA-2: Di (2,2,3,3,4,4,5,5-octafluoropentyl) sulfosuccinate / sodium salt Salt HA-1: 2,4-dichloro-6-hydroxy-s-triazine
sodium

[0164]

[Chemical 43]

[0165]

[Chemical 44]

[0166]

[Chemical formula 45]

Separately, the compound (C-
Samples 28 to 34 were prepared in exactly the same manner except that 1) was changed to compounds (C-2), (C-3) and the fog agent represented by the general formula (I) of the present invention shown in Table 3. Created.

Each of the obtained samples was exposed through an optical wedge using a sensitometer and processed in the processing steps shown below.

(Processing-1) Processing process time Temperature Color development 2 minutes 33 ° C Bleach fixing 40 seconds 33 ° C Stability 20 seconds 3 times 33 ° C Dry 30 seconds 60-80 ° C Color developer-1 Diethylenetriamine 5 Acetic acid 2.0 g 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 30.0 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Water was added to make the total volume 1 liter, and the pH was adjusted to 10.5 with potassium hydroxide or sulfuric acid.

Bleach-fixing solution Ammonium thiosulfate (54% aqueous solution) 150 cc Sodium sulfite 15 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Sodium ethylenediaminetetraacetate (dihydrate) 4 g Glacial acetic acid 8.61 g Water was added to bring the total volume to 1 liter. The pH was adjusted to 5.4 with aqueous ammonia or hydrochloric acid.

Stabilizer 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.6cc Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Ammonia water 2.5cc Nitrilotriacetic acid / 3Na 1.0g 5-chloro-2-methyl- 4-isothiazolin-3-one 50mg 2-octyl-4-isothiazolin-3-one 50mg Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Add water to bring the total volume to 1 liter and add hydroxylation. The pH was adjusted to 7.5 with potassium or hydrochloric acid.

(Process-2) The same as Process-1 except that the pH of the color developing solution was adjusted to 11.0.

Sensitometry was performed on the obtained image, and the maximum density Dmax and the minimum density Dmin of the magenta image were evaluated. Table 3 shows the results.

[0174]

[Table 3]

As is clear from Table 3, Samples 30 to 34 containing the fog agent of the present invention have a larger maximum concentration even at low pH treatment than Samples 27 to 29 containing the comparative compound which is a known fog agent. And gives a good positive image with a small minimum density.

Example 4 Samples 35 to 42 were prepared in the same manner as in Example 3 except that the compounds shown in Table 4 were used.

Each sample was exposed and treated in the same manner as in Example 3.
Treated with 1. The minimum density of the obtained magenta image is Dmi
Let n.

On the other hand, the raw sample (sample before exposure and development) was heated to 50 ° C.
-It was stored under the condition of 80% RH for 3 days and forcedly deteriorated. Then, it was exposed and developed as described above. The minimum density of the magenta image at this time is D'min.

Table 4 shows the values of Dmin and D'min.

[0180]

[Table 4]

As is clear from Table 4, the samples 38 to 42 containing the fog agent of the present invention showed a minimum increase in concentration after storage as compared with the samples 35 to 37 containing the comparative compound which is a known fog agent. Low, excellent stability of raw samples over time.

Example 5 (Preparation of silver halide emulsion) 70 mol% of silver chloride and 30 mol of silver bromide
A silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr were mixed by a controlled double jet method to grow a silver halide grain so as to have a mol% silver halide composition. At this time, the mixing was carried out under the conditions of 36 ° C., pAg 7.8 and pH 3.0, and 2 × 10 ⁻⁷ mol of Na ₂ RhCl ₆ was added per 1 mol of silver during grain formation. After that, desalting was carried out with a modified gelatin treated with phenyl isocyanate to give the following compounds [A] [B] [C]
Add a bactericide consisting of a mixture of and ossein gelatin,
Redistributed. The obtained emulsion has an average grain size of 0.2 μm and a coefficient of variation
The emulsion consisted of 10% cubic grains. To the emulsion thus obtained, 30 mg of S-1 and 60 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added per mol of silver, and 5 mg of chloride was added per mol of silver. Gold acid and 0.5 mg of sulfur flower were added, and chemical ripening was carried out at 60 ° C. for 80 minutes under the conditions of pH 5.8 and pAg 7.5. After aging, 4-hydroxy-6-methyl-1,3,3
900 mg of a, 7-tetrazaindene was added per mol of silver, and further 300 mg of KI and 350 mg of S-2 were added.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was used, in which the amount of gelatin was 2.6 g / m ² and the amount of silver was 3.2 g / m ^2.
And a 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. Apply a backing layer according to the following prescription (3) so that the amount of gelatin becomes 3.1 g / m ² , and further apply a protective layer of the following prescription (4) so that the amount of gelatin becomes 1 g / m ² . A raw sample was obtained by coating.

Further, the raw sample was stored at 60 ° C. and 75% RH for 7 days to obtain a forced deterioration sample.

Formulation (1) [Silver halide emulsion layer composition] Gelatin 2.6 g / m ² Silver halide emulsion Silver amount 3.2 g / m ² Antifoggant: Adenine 25 mg / m ² Stabilizer: 1-phenyl-5- Mercaptotetrazole 2 mg / m ² 5-Nitroindazole 10 mg / m ² Nucleating agent: Compound of Table 5 3 × 10 ⁻⁵ mol / m ² Nucleation accelerator: Compound of Table 5 1 × 10 ⁻⁴ mol / m ² Polymer Latex 1 1.0 g / m
² Water-soluble polymer A 100mg
/ M ² Colloidal silica 0.5 g / m ² p-Nonylphenol 50 mol adduct of ethylene oxide 45 mg / m ² Surfactant: saponin 0.1 g / m ² : sulfosuccinic acid i-pentyl decyl sodium salt 8 mg / m ² hard Membrane agent: HA-1 60 mg / m ² formulation (2) [Emulsion protective layer composition] Gelatin 1.0 g / m ² Matting agent: Silica 20 mg / m ² polymer latex 2 0.5 g / m ^{2 with an} average particle size of 3.5 μm Surfactant: Di (2-ethylhexyl) sulfosuccinate sodium salt 10mg / m ² p-heptadecylfluorononylbenzenesulfonate potassium 2mg / m ² Accelerator: Hydroquinone 50mg / m ² 1-phenyl-4-hydroxymethyl -4-Methyl-3-pyrazolidone 5 mg / m ² Hardener: Formalin 30 mg / m ²

[0186]

[Chemical formula 46]

Formulation (3) [Backing layer composition]

[0188]

[Chemical 47]

Gelatin 3.1 g / m ² Surfactant: Sodium dodecylbenzenesulfonate 50 mg / m ² (4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Polymethyl methacrylate 50 mg / average particle size 4.0 μm / m ² Surfactant: sulfosuccinate di (2-ethylhexyl) sodium salt 10 mg / m ² Hardener: Glyoxal 25 mg / m ² HA-1 35 mg / m ^{2 The} sample obtained was evaluated by the following method. .

(Expansion) Manuscript Preparation Dainippon Screen Scanner SG-747 and Konica New RST System Scanner Film RSP-
3 was used to create a transparent image of a person consisting of halftone dots and a step wedge in which halftone% was changed stepwise. The number of screen lines at this time was 150 lines / inch.

Photographing The above document was set on a fine zoom C-880F manufactured by Dainippon Screen Co., Ltd. so that the stretching magnification was 120% and exposed. At this time, the exposure was performed so that 95% of the step wedge of the original became 5%. The exposed sample was developed by the method described below.

Evaluation Method Good gradation reproducibility (difficulty in dot collapse) of the shadow part of the sample obtained by adjusting the exposure amount and combining the dot% on the small dot side (highlight part). Five-level evaluation was performed in order from the thing. 5 is good and 1 is inferior. The practically usable level was set to 3.

Processing was performed under the following conditions with a rapid automatic developing machine using a developing solution and a fixing solution having the compositions shown below.

Developer formulation Sodium sulfite 50 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 0.85 mg Diethylenetriaminepentaacetic acid 1.5 g Boric acid 8 g Potassium bromide 4 g Potassium carbonate 55 g 5-Methylbenzotriazole 200 mg Benzotriazole 83 mg Hydroquinone 20g Potassium hydroxide pH 10.3 At the time of use, water was added to make 1 liter.

Fixer formulation Ammonium thiosulfate (59.5% w / v aqueous solution) 830 cc Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% w / v aqueous solution) 82 g Citric acid (50% w / v aqueous solution) ) 15.7 g Gluconic acid (50% w / w aqueous solution) 8.55 g Aluminum sulfate (48% aqueous solution) 13 cc Glutaraldehyde 3 g Sulfuric acid Amount to bring pH to 4.6 when used. Water was added to make 1 liter.

[0196] (Evaluation of Black Pins) Unexposed Film The film was processed under the developing and fixing processing conditions described above, and the processed film was observed with a magnifying glass of 50 times to evaluate the degree of occurrence of black pins. The highest rank is "5" when there is no black pin in the halftone dot, and the rank is "4" according to the degree of occurrence of black pin in 2mm x 2mm.
The evaluation was made in order of "3", "2" and "1". Incidentally, in the ranks "1" and "2", the black pin is also large, which is a level unfavorable for practical use.

The results are shown in Table 5.

[0198]

[Table 5]

[0199]

[Chemical 48]

From the results shown in Table 5, it can be seen that the samples of the present invention are excellent in reproducibility of halftone dots such as black pins and stretch marks even after storage of raw samples.

Example 6 Samples 57 to 65 were prepared in the same manner except that the compounds shown in Table 6 were used as the fogging agent in Example 4.

Each sample was exposed and treated in the same manner as in Example 4.
Treated with 1. The minimum density of the obtained magenta image is Dmi
Let n.

On the other hand, the raw sample was placed under the condition of 50 ° C. and 80% RH for 7 days.
Let D ″ min be the minimum density of a magenta image when it is stored for days and forcedly deteriorated, and similarly exposed and developed.

Table 6 shows the values of Dmin and D ″ min.

[0205]

[Table 6]

As is clear from Table 6, samples 61 to 65 containing the fog agent of the present invention are samples 57 to 57 containing known fog agents.
Compared to 60, the minimum concentration did not increase even after storage over time, and the stability of raw samples over time was excellent.

[0207]

According to the present invention, there is provided a silver halide photographic light-sensitive material having high tone and excellent halftone dot quality after storage of a raw sample, less fog, good halftone dot quality in the stretched state, and high sensitivity. We were able to. 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
A good positive image having a large maximum density and a small minimum density was obtained by fog development for a relatively short time, and a light-sensitive material in which the minimum density did not increase even after storage with time could be provided.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, containing at least one compound represented by the following general formula (I). Photosensitive material. [Chemical 1] In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₂ represents a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group. R represents a hydrogen atom or a block group. L represents an alkylene group or an alkenylene group. However, at least two rings are included in the R ₁ -SL part. Each of these rings may be bonded with a bond and / or an aliphatic group. J ₁ and J ₂ each represent a linking group, and n represents 0 or 1. X represents an aromatic residue or a heterocyclic residue. 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.