JPH0675320A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain photographic sensitive material capable of obtaining high contrast and sufficient max. density and processing with a stable developer without causing development irregularity or fog by incorporating specified two kinds of compds. into the silver halide emulsion layer. CONSTITUTION:This silver halide photographic sensitive material has a silver halide emulsion layer containing at least 90mol% silver chloride and 5X10<-7>-2X10<-4>mol water-soluble rhodium salt par one mol of silver chloride on a supporting body. The silver halide emulsion layer and other hydrophilic colloid layers contain a compd. expressed by formula I. The silver halide emulsion layer contains at least one compd. expressed by formula II and at least one compd. expressed by formula III. In the formulae II and III, M is a hydrogen atom or cation, Z is a heterocyclic residue containing at least one nitrogen atom, R4-R6 are hydrogen atoms, alkyl groups, alkenyl groups, or alkylthio groups, and R7 is a hydroxy groups or mercapto 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 an ultra-high contrast light room light-sensitive material mainly used in the printing plate making industry.

[0002]

2. Description of the Related Art Recently, in the field of printing, due to the complexity of printed materials and the development of scanners, it has been desired to improve the efficiency of the returning work process. Therefore, a photographic film with a low sensitivity of about 10 ^-4 to 10 ^-5 has been developed compared to the conventionally used return film, and the return film can be handled in a bright room (under a white fluorescent lamp excluding ultraviolet rays). It is practically used as a film, that is, a light-sensitive material for a bright room. The performance required for such a light-sensitive material for a bright room is that it can be handled for a long time in a light room and has a high sensitivity to a printer light source, and also a conventional light-sensitive material for a dark room. It has a sufficient maximum density with moderate or higher hardness.

It is known in the art to use a hydrazine compound in order to have a high contrast and a sufficient maximum concentration. Addition of a hydrazine compound to a silver halide photographic emulsion or a developing solution is described in US Pat. No. 3,730,727 (developing solution combining ascorbic acid and hydrazine) and US Pat. No. 3,227,552. (Use of hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (containing β-monophenylhydrazide of aliphatic carboxylic acid as a stabilizer of silver halide sensitizer) No. 2,419,975, and "The Theory of Photographic process", 3rd edition (1966) by Mees, page 281.

Among these, especially US Pat. No. 2,41
No. 9,975, it is disclosed that a high contrast negative image is obtained by adding a hydrazine compound. That is, when a hydrazine compound is added to a silver chlorobromide emulsion and development is performed with a developer having a high pH such as 12.8, it is possible to obtain extremely hard photographic characteristics with a gamma (γ) of more than 10.
Have been described. However, a strong alkaline developer having a pH close to 13 is easily oxidized by air, is unstable, and cannot withstand long-term storage or use.

In contrast, US Pat. No. 4,168,9
77, 4,224,401, 4,243,73
No. 9, No. 4,269, 929, No. 4,272, 614
No. 4,323,643 and the like disclose a silver halide photographic light-sensitive material which gives a very hard negative negative photographic property by using a stable developing solution, and the acylhydrazine compound used for them is It is known that nitrogen gas is generated during the development process, and this gas collects in the film to form bubbles, which may impair the photographic image.

Therefore, for the purpose of reducing the generation of air bubbles and simultaneously reducing the cost of producing a light-sensitive material, hydrazine which is hard in tone and has a sufficient maximum density even with a small amount of addition and which is less likely to cause uneven development or sand fog. Silver halide photographic light-sensitive materials containing compounds are disclosed in JP-A-62-178246 and 62-62.
-180361, 62-275247, 63-
253357 and the like.

Further, when this photographic light-sensitive material is treated with a developer whose activity has increased due to fatigue over time, nucleation and infectious development by a hydrazine compound is promoted, resulting in an increase in sensitivity, a marked increase in halftone dot area ratio, and innumerable sand. It was found that fog and the like occurred. This phenomenon occurs regardless of which hydrazine is used, and therefore a countermeasure has been required.

To solve this problem, it has been proved effective to add the compound having a mercapto group of the present invention to the emulsion layer. However, in the light-sensitive material containing the compound having a mercapto group, the light-sensitive material for bright room is used. It was found that there is a problem with the safety of white fluorescent lamps except for ultraviolet light, which is used as a safety light, in the material, fog occurs in the normal working time, and the dot area ratio remarkably increases.

[0009]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material having a high contrast and a sufficient maximum density.

Secondly, the object of the present invention is to provide a silver halide photographic light-sensitive material which can be processed with a stable developing solution and which causes less development unevenness and sand fog.

Thirdly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is less susceptible to increase in sensitivity and less in sand fog even if it is processed with a developer having increased activity due to fatigue over time. .

A fourth object of the present invention is to provide a light-sensitive photographic light-sensitive material which can be handled in a light room for a long time.

[0013]

The objects of the present invention are to provide at least 90 mol% of silver chloride on a support, and 5 × 10 ^-7 to 2 × 10 ^-4 mol of a water solution per mol of silver halide. Having at least one light-sensitive silver halide emulsion layer having silver halide grains containing a photosensitive rhodium salt, the silver halide emulsion layer or another hydrophilic colloid layer having the following chemical formula 4
In a silver halide photographic light-sensitive material containing a compound represented by the following formula, at least one compound represented by the following chemical formula 5 and at least 1 compound represented by the following chemical formula 6 are contained in the silver halide emulsion layer. It was achieved by a silver halide photographic light-sensitive material characterized by containing one of them.

[0014]

[Chemical 4]

[Wherein Ar represents an aryl group, and R
Is a group represented by -OR ₁ or -N (R ₂ )
It represents a group represented by (R ₃ ). R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group. R ₂ , R ₃
Each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted pyridinium group. Further, R ₂ and R ₃ may be linked to each other to form a ring. ]

[0016]

[Chemical 5]

[In the chemical formula 5, M represents a hydrogen atom or a cation, Z represents a heterocyclic residue containing at least one nitrogen atom,
The heterocycle residue may be further condensed. ]

[0018]

[Chemical 6]

[Wherein R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or an alkylthio group. , R ₄ and R ₅ may together form a 5- or 6-membered ring. However, the total number of carbon atoms of R ₄ and R ₅ is 3 or more. R ₇ represents a hydroxy group or a mercapto group. ]

In the chemical formula 4, the aryl group represented by Ar is specifically a phenyl group which may have a substituent, or a naphthyl group, and examples of the substituent include an alkyl group, Aryl group, hydroxyl group, halogen atom, alkoxy group, alkylthio group, aryloxy group, alkenyl group, amino group, acylamino group, sulfonamide group, alkylideneamino group, ureido group, thiourea group, thioamide group, heterocyclic group, or These combinations and the like can be mentioned.

Further, Ar may have a ballast group incorporated therein which is practically used in a non-moving photographic additive such as a color coupler. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photographic properties, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group and a phenoxy group.

In Chemical formula 4, R represents a group represented by —OR ₁ or a chemical group represented by Chemical formula 7.

[0023]

[Chemical 7]

R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group.

R ₂ and R ₃ are each independently a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a pyridinium group represented by Chemical formula 8. Also, R
₂ and R ₃ may combine with each other to form a ring.

[0026]

[Chemical 8]

R ₈ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group. R ₉ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. X ⁻ represents an anion.

Specific examples of the compound represented by Chemical formula 4 are shown below. However, the present invention is not limited to the following compounds.

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

[0045]

[Chemical 25]

[0046]

[Chemical formula 26]

[0047]

[Chemical 27]

[0048]

[Chemical 28]

[0049]

[Chemical 29]

[0050]

[Chemical 30]

[0051]

[Chemical 31]

[0052]

[Chemical 32]

[0053]

[Chemical 33]

[0054]

[Chemical 34]

[0055]

[Chemical 35]

[0056]

[Chemical 36]

[0057]

[Chemical 37]

[0058]

[Chemical 38]

[0059]

[Chemical Formula 39]

[0060]

[Chemical 40]

[0061]

[Chemical 41]

[0062]

[Chemical 42]

[0063]

[Chemical 43]

[0064]

[Chemical 44]

[0065]

[Chemical formula 45]

[0066]

[Chemical formula 46]

[0067]

[Chemical 47]

[0068]

[Chemical 48]

[0069]

[Chemical 49]

[0070]

[Chemical 50]

[0071]

[Chemical 51]

[0072]

[Chemical 52]

[0073]

[Chemical 53]

[0074]

[Chemical 54]

[0075]

[Chemical 55]

[0076]

[Chemical 56]

[0077]

[Chemical 57]

[0078]

[Chemical 58]

[0079]

[Chemical 59]

[0080]

[Chemical 60]

[0081]

[Chemical formula 61]

[0082]

[Chemical formula 62]

[0083]

[Chemical formula 63]

[0084]

[Chemical 64]

[0085]

[Chemical 65]

[0086]

[Chemical formula 66]

[0087]

[Chemical formula 67]

[0088]

[Chemical 68]

[0089]

[Chemical 69]

[0090]

[Chemical 70]

[0091]

[Chemical 71]

[0092]

[Chemical 72]

[0093]

[Chemical formula 73]

[0094]

[Chemical 74]

[0095]

[Chemical 75]

[0096]

[Chemical 76]

[0097]

[Chemical 77]

[0098]

[Chemical 78]

[0099]

[Chemical 79]

[0100]

[Chemical 80]

[0101]

[Chemical 81]

[0102]

[Chemical formula 82]

[0103]

[Chemical 83]

[0104]

[Chemical 84]

[0105]

[Chemical 85]

[0106]

[Chemical 86]

[0107]

[Chemical 87]

[0108]

[Chemical 88]

[0109]

[Chemical 89]

[0110]

[Chemical 90]

[0111]

[Chemical Formula 91]

[0112]

[Chemical Formula 92]

[0113]

[Chemical formula 93]

[0114]

[Chemical 94]

[0115]

[Chemical 95]

[0116]

[Chemical 96]

[0117]

[Chemical 97]

[0118]

[Chemical 98]

[0119]

[Chemical 99]

The compound represented by Chemical formula 4 in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers.
Since the content of the compound of formula 4 of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the developing conditions, the appropriate content can vary over a wide range. A range of about 5 × 10 ⁻⁶ to 8 × 10 ⁻² mol per mol of silver in the silver halide emulsion is practically useful, and more preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol. Is good.

In Chemical formula 5, M represents a hydrogen atom or a cation (for example, an alkali metal ion, an ammonium ion, etc.), and the heterocyclic residue represented by Z may be further condensed. , Imidazole, triazole, tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzoxazole, benzthiazole, thiadiazole, oxadiazole, benzselenazole, azaindene (eg, triazaindene, tetrazaindene, pentazaindene, etc.), etc. Is preferred.

Further, these heterocyclic residue and condensed ring may be substituted with an appropriate substituent. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, hydroxyethyl group, etc.), alkenyl group (eg, allyl group, etc.), aralkyl group (eg, benzyl group), aryl group (eg, phenyl group, naphthyl group, etc.) ), A heterocyclic residue (such as a pyridine group), a halogen atom, a mercapto group, a cyano group, a carboxyl group, a sulfo group, a hydroxy group, an amino group, a nitro group, and an alkoxy group (such as a methoxy group).

Specific examples of the compound represented by Chemical formula 5 are shown below. However, the present invention is not limited to the following compounds.

[0124]

[Chemical 100]

[0125]

[Chemical 101]

[0126]

[Chemical 102]

[0127]

[Chemical 103]

[0128]

[Chemical 104]

[0129]

[Chemical 105]

[0130]

[Chemical formula 106]

[0131]

[Chemical formula 107]

[0132]

[Chemical 108]

[0133]

[Chemical 109]

[0134]

[Chemical 110]

The compound represented by Chemical formula 5 in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers.
Since the content of the compound of formula 5 of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can be varied over a wide range. A range of about 5 × 10 ^{−6 to} 5 × 10 ⁻² moles is practically useful per mole of silver in the silver halide emulsion, more preferably 1 × 10 ^{−4 to} 3 × 10 ⁻² moles. Is good.

In the present invention, the tetrazaindene compound represented by Chemical formula 6 is a 4-hydroxy or 4-mercapto-compound having a total of 3 or more carbon atoms in the substituents at the 5th and 6th positions.
It is 1,3,3a, 7-tetrazaindene.

Specific examples of the compound represented by Chemical formula 6 are shown below. However, the present invention is not limited to the following compounds.

[0138]

[Chemical 111]

[0139]

[Chemical 112]

[0140]

[Chemical 113]

[0141]

[Chemical 114]

[0142]

[Chemical 115]

[0143]

[Chemical formula 116]

[0144]

[Chemical 117]

[0145]

[Chemical 118]

[0146]

[Chemical formula 119]

The compound represented by Chemical formula 6 in the photographic material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers.
Since the content of the compound of formula 6 of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can be varied over a wide range. A range of about 6 × 10 ^{-6 to} 6 × 10 ^-2 mol is practically useful per mol of silver in the silver halide emulsion, and more preferably a range of 2 × 10 ^-4 to 4 × 10 ^-2 mol. Is good.

A silver halide photographic light-sensitive material containing a hydrazine compound containing a compound having a mercapto group is disclosed in JP-A-60-153039 and 63-10.
3232 and the like, all of them are compounds having a mercapto group that act as an organic antifoggant, and are only white except ultraviolet light used as a safe light in a light-sensitive material for a bright room. There is a problem with the safety of fluorescent lamps.

On the other hand, the addition of a tetrazaindene compound into a silver halide photographic light-sensitive material has been described as "photographic chemistry".
(Photo Industry Co., Ltd.) is a technique known to those skilled in the art, and a technique for adding a hydroxytetrazaindene compound to a silver halide photographic emulsion containing a hydrazine compound is disclosed in Sho 53-8471
4 and 64-65541. However, all of these are results when a hydrazine derivative different from the present invention is used, and further show effects different from the present invention.

That is, the effect of the present invention is first exhibited by the combination of the hydrazine derivative represented by Chemical formula 4 and the compound having a mercapto group represented by Chemical formula 5 and the specific benzotriazole compound represented by Chemical formula 6 in the present invention. (Even the tetrazaindene compound that is very commonly used in the photographic industry, 4-hydroxy-6-methyl-1,3,
The effect of the present invention cannot be obtained with 3a, 7-tetrazaindene. ), Which is a completely new effect that cannot be expected from the prior art.

The silver halide used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is silver chloride or silver chlorobromide, silver chlorobromoiodide, or silver chlorobromide containing at least 90 mol% of silver chloride.
Silver chloroiodide or the like can be used. Preferably, silver chloride, silver chlorobromide having a silver bromide content of 5 mol% or less, or silver chloroiodide having a silver iodide content of 1 mol% or less is preferred. The morphology, crystal habit, size distribution, etc. of the silver halide grains are not particularly limited, but the average grain size is 0.1 to 0.4 μm, and 90% or more of all grains are ± 10 of the average grain size. Those having a particle size in the range of% are preferable. The silver halide emulsion may be prepared by any known method such as forward mixing, reverse mixing and simultaneous mixing.

As the water-soluble rhodium salt used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention, conventionally known ones can be used. Typical examples are rhodium monochloride, rhodium dichloride and rhodium trichloride. Chlorides, rhodium ammonium chloride and the like are used.
Generally, the water-soluble rhodium salt is preferably used at the time of precipitation of silver halide or physical ripening, but may be at any time thereafter. The water-soluble rhodium salt is effective in the range of 5 × 10 ⁻⁷ to 2 × 10 ⁻⁴ mol per mol of silver halide, and more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻ per mol of silver halide. A range of ⁴ moles is good.

In addition to the rhodium salt, an iron compound such as a noble metal salt such as an iridium salt or a red blood salt may be allowed to be present during physical ripening or nucleation of silver halide grains.

The emulsion that had been physically ripened was desalted and then
It is preferable that the necessary additives are added before coating, but the desalting treatment can be omitted.

The photosensitive material of the present invention may be provided with an overcoat layer, an intermediate layer, a backcoat layer, an undercoat layer and other hydrophilic colloid layers in addition to the photosensitive emulsion layer. A matting agent may be contained in these layers.

As the binder or protective colloid that can be used in the emulsion layer, overcoat layer, intermediate layer, backcoat layer and the like of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic substances are used. A sex colloid can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. It is possible to use various kinds of synthetic hydrophilic polymer substances such as a partial or acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and other single or copolymers. . Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No. 16, P30 (19).
The enzyme-treated gelatin as described in 66) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin can also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chrome alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds,
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds, active halogen compounds (2,4
-Dichloro-6-hydroxy-S-triazine etc.),
Etc. can be used alone or in combination.

The photographic emulsion used in the present invention contains an emulsion layer, an overcoat layer, a backing layer, etc. for the purpose of enhancing the image quality due to irradiation, halation and the like, the character removal performance and other performances required in the printing plate making industry. Other hydrophilic colloid layers of can include filter dyes known to those skilled in the art.

Further, in a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement of slipperiness, an emulsion dispersion, an adhesion prevention and an improvement of photographic characteristics (for example, , Development acceleration, contrast enhancement, and sensitization) may be included for various purposes. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic surface active agent containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group, such as an alkylcarboxylic acid salt, an alkyl sulfuric acid ester, an alkyl phosphoric acid ester, etc. Agents: amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium What cationic surfactant can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid,
A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

Any support known in the art can be used in the photographic light-sensitive material used in the present invention. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (for example, polyethylene, polypropylene, etc.) laminated paper, polystyrene film, polycarbonate film, and metal plate such as aluminum. These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to undercoating treatment by a known method.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing sufficient sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Especially 10.5-1
With the developer of 2.3, a super-high contrast negative image can be sufficiently obtained. The developing agent is not particularly limited, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. In addition to the above, the developer contains a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, bromide, iodide, and organic antifoggant (particularly preferably,
Development inhibitors or antifoggants such as nitroindazoles or benzotriazoles). Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a film hardener, a film silver stain inhibitor (for example, 2-mercaptobenzimidazole acid), etc. May be included. Specific examples of these additives are described in Research Disclosure No. 176-1.
7643 and the like.

In the present invention, a system may be adopted in which a developing agent is incorporated in the light-sensitive material and processing is carried out with an alkaline activator solution. (JP-A-57-129436, 57-129433, 57-129434, 5)
7-129435, U.S. Pat. No. 4,323,643, etc.). The treatment temperature is usually selected from 18 ° C to 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. It is preferable to use an automatic processor for photographic processing. In the present invention, the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is 60 seconds to 120 seconds.
Even if it is set to seconds, it is possible to obtain photographic characteristics of super-hard negative tone.

[0164]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the description.

Example 1 A gelatin silver chloride emulsion containing 6.4 × 10 ⁻⁶ mol / mol Ag of rhodium dichloride consisting of cubic crystals having an average particle size of 0.13 μm was prepared by the double jet method and subjected to flocculation. The hydrazine compound of the present invention shown in Table 1 and Table 2 is divided into 1 × 10 ⁻³ mol / mol Ag and the present invention represented by Chemical Formula 5 3 × 10 ⁻³ mol / mol Ag, the tetrazaindene compound of the present invention represented by Chemical formula 6 and its comparative compound (Chemical formula 120) are 6 × 10 ⁻³ mol / mol A
g, and further 2-hydroxy-4,6-dichloro-1,3
Polyethylene with 5-triazine sodium salt and a backing agent (Oxonol Yellow from Hoechst 200 mg / m ² , a gelatin solution containing a hardening agent, a surfactant and a matting agent) after adding a surfactant of Chemical formula 121 5g / m ² with silver nitrate and 3g / m with gelatin on terephthalate film
^It was applied so as to be ² . As a protective layer, 1 g / m ^{2 of} gelatin, a surfactant, a hardener and a matting agent were added and coated thereon to prepare the samples shown in Tables 1 and 2.

[0166]

[Chemical 120]

[0167]

[Chemical 121]

These films were exposed through a sensitometric wedge with a bright room printer (P-627FM, manufactured by Dainippon Screen Mfg. Co., Ltd.) and then developed with a developer having the following composition at 38 ° C. for 20 seconds. Fixing, washing with water,
Dried. An automatic processor (Dainippon Screen Mfg. Co., Ltd., LD-221QT) was used for this treatment. From this, gamma was measured. Gamma has an optical density of 1.0 to
It was measured by tan θ of the straight line portion of 2.5.

Further, in order to test the safety against safelight light, the following two kinds of tests were conducted. First, 5
It was exposed and developed so that 0% halftone dot document became 50%, and this was used as a standard sample. On the other hand, after leaving for 20 minutes under the bright room light from which 300 Lux of ultraviolet light has been removed, that is, under the fluorescent light of Toshiba FL40SWNU, it is exposed and developed with the same exposure amount as the standard sample, and the change amount of halftone dot% (safelight is If it becomes x% when irradiated, ΔDot = x-50)
Was measured. Further, the film was exposed to the same safelight for 60 minutes from the film surface and then developed to measure the change in Dmin as safelight fog.

Further, the following test was conducted in order to investigate the characteristics when treated with the developer whose activity was increased due to fatigue over time. Similarly to the above-described safety test for safelight light, each light-sensitive material was first exposed so that 50% of halftone dot originals would be 50%, and developed with a developer in a new liquid state, which was used as a standard sample. did. The standard sample was exposed with the same exposure amount and left in an open container for one week to develop, and the change in halftone dot percentage was measured in the same manner as above.

<Developer> Hydroquinone 50.0 g N-methyl-p-aminophenol 1 / 2H ₂ SO ₄ 0.3 g Sodium hydroxide 18.0 g 5-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g EDTA · 2Na 1 0.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzene imidazole-5-sulfonic acid 0.2 g 3- (5-Mercaptotetrazole) benzene sodium sulfonate 0.2 g Sodium toluenesulfonate 8. Add 0 g water and adjust to pH 11.8 with 1 l potassium hydroxide.

The results are shown in Tables 1 and 2.

[0173]

[Table 1]

[0174]

[Table 2]

From the results of Tables 1 and 2, the photographic light-sensitive materials obtained by combining the compounds of Chemical formulas 4, 5, and 6 shown in the present invention are similarly excellent as compared with the photographic light-sensitive materials of Comparative Examples. For bright rooms, where the halftone dot area ratio does not increase even when processed with a developer that has become active due to fatigue over time, while maintaining good image and hard photographic characteristics, and has good safety against safelight. It can be seen that a photographic light-sensitive material can be obtained.

[0170]

EFFECTS OF THE INVENTION According to the present invention, it has a high contrast and a sufficient maximum density and can be processed with a stable developer, and development unevenness and sand fog do not occur, and it is stable even with a fatigue developer over time.
Furthermore, a negative type silver halide photographic light-sensitive material which can be handled in a bright room for a long time can be obtained.

Claims (1)

[Claims] 1. At least 90 mol% of silver chloride on a support, and 5 × 10 ⁻⁷ to 2 × per mol of silver halide.
It has at least one photosensitive silver halide emulsion layer having silver halide grains containing 10 ⁻⁴ mol of a water-soluble rhodium salt, and the silver halide emulsion layer or another hydrophilic colloid layer is In a silver halide photographic light-sensitive material containing a compound represented by formula 1, at least one compound represented by formula 2 below and at least one compound represented by formula 3 below are contained in the silver halide emulsion layer. A silver halide photographic light-sensitive material containing one of them. [Chemical 1] [In Chemical Formula 1, Ar represents an aryl group, and R is -OR ₁
Or a group represented by —N (R ₂ ) (R ₃ ). R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group. R ₂ and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted pyridinium group. Further, R ₂ and R ₃ may be linked to each other to form a ring. ] [Chemical 2] [In Chemical Formula 2, M represents a hydrogen atom or a cation, Z represents a heterocyclic residue containing at least one nitrogen atom, and the heterocyclic residue may be further condensed. ] [Chemical 3] [Wherein R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or an alkylthio group, and R ₄ And R ₅ may together form a 5- or 6-membered ring. However, the total number of carbon atoms of R ₄ and R ₅ is 3 or more. R ₇ represents a hydroxy group or a mercapto group. ]