JP2847571B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic light-sensitive material without deteriorating photographic characteristics such as sensitivity and contrast even in rapid processing, and using a film. The present invention relates to a silver halide photographic light-sensitive material which suppresses generation of safelight fog during handling.

[Background of the Invention]

In recent years, efforts have been made to increase the processing speed of silver halide photographic light-sensitive materials in order to increase work efficiency and speed. For example, in the field of medical X-ray films, an ultra-rapid processing system of several tens of seconds has been developed. Established.

Conventionally, the sensitivity of silver halide photographic materials has been increased,
Many techniques for improving developability have been reported for a long time. For example, US Patents using organic thioether compounds
3,021,215, 3,038,805, 3,271,157, 3,53
Nos. 1,289 and 3,574,628 and JP-A-53-57817 using an organic tellurium compound are disclosed.

The present applicant has already proposed sensitization of silver halide emulsions with an organic tellurium compound and an organic selenium compound and improvement of rapid processing properties.

However, subsequent studies have revealed that the silver halide photographic light-sensitive material using the above organic compound has a disadvantage that fog is liable to occur due to safelight used in a dark room operation.

It has been reported in Japanese Patent Application Laid-Open No. 2-110541 that this safe light fog, unlike ordinary fog, is also caused by the silver halide emulsion grains themselves, and tends to occur more frequently in, for example, a core / shell type silver halide emulsion. ing.

Therefore, there has been a strong demand for improvement in stability against safelight without impairing sensitivity and developability.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having excellent sensitivity and contrast in rapid development processing and excellent storage stability over time.

A second object of the present invention is to handle a film.
An object of the present invention is to provide a silver halide photographic light-sensitive material having a rapid processability without fogging caused by a safelight used in a dark room. Other objects will be apparent from the following description.

[Configuration of the invention]

As a result of various studies, the present inventors have found that these objects can be achieved as follows, and have accomplished the present invention.

That is, at least one side of the support
In a silver halide photographic material having a silver halide emulsion layer structure, at least one compound represented by the following general formula (I), (II) or (III) is contained in the silver halide emulsion layer. This is achieved by a silver halide photographic light-sensitive material which contains at least one compound represented by the following general formula [IV] in the silver halide photographic light-sensitive material constituting layer.

In the general formula (I) Y ₁ -Te-Y ₂ formula, Y _1, Y ₂ may represent the same or different and may be substituted or unsubstituted aliphatic group, at least one of which, hydroxy group, amino group , Ammonium group, ether group, thioether group, selenoether group, mercapto group, carbamoyl group, carbonamide group, sulfonyl group, sulfamoyl group, sulfonamide group, sulfonyloxy group,
Acyloxy group, ureido group, thioureido group, thioamide group, oxysulfonyl group, oxycarbonylamino group, sulfonic acid or a salt thereof, sulfinic acid or a salt thereof,
Phosphoric acid or a salt thereof, a phosphate group, a phosphino group,
Or a group substituted with a heterocyclic group.

Formula II _{Y 3 -R 1 -Se-R 2} -Y 4 in the general formula (III) Y ₃ -R ₁ -Se-R ₃ formula, R _1, R ₂ are each independently a carbon atom, a nitrogen atom , An oxygen atom, a sulfur atom, and a selenium atom, and represents a divalent group, and R ₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group.

Y ₃ and Y ₄ are each a hydroxy group, an amino group, an ammonium group, an ether group, a thioether group, a selenoether group, a carbamoyl group, a carbonamide group, a sulfonyl group, a sulfamoyl group, a sulfonamide group, a sulfonyloxy group, and an acyl group. , An acyloxy group, a ureido group, a thioureido group, an oxysulfonyl group, an oxycarbonyl group, an oxycarbonylamino group, a sulfone group, a sulfonic acid or a salt thereof, a carboxylic acid or a salt thereof, or a heterocyclic group.

General formula (IV) In the formula, R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkenyl group, or Represents R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ¹ and R ² may combine with each other to form a ring.

M represents a hydrogen atom, an alkali metal atom or an ammonium group.

 Next, the compound of the formula (I) will be described in detail.

In the formula, the aliphatic group of Y ₁ and Y ₂ refers to an alkyl group, an alkenyl group and a cycloalkyl group, and the alkyl group has 1 to 30 carbon atoms (eg, methyl, ethyl, propyl, n-butyl). , Sec-butyl, t-butyl, n-hexyl, n-octyl, n-dodecyl, n-
Hexadecyl, n-octadecyl, isostearyl, eicosyl, etc.),
Twenty alkenyl groups (eg, allyl, butenyl, octenyl, dodecenyl, oleyl groups, etc.) are included. Examples of the cycloalkyl group include a cyclopropyl, cyclopentyl, cycloheptyl, cyclododecyl group and the like.

As the aliphatic group represented by Y ₁ and Y ₂ , an amino group (eg, amino, dimethylamino, diethylamino group, etc.), an ammonium group (eg, trimethylammonium group), an ether group (eg, methoxy, phenoxy group, etc.), a thioether group (Eg, methylthio, phenylthio group, etc.), selenoether group (eg, methylseleno, phenylseleno group, etc.), carbamoyl group (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl group, etc.), carbonamide group (eg, acetamido, benzoamide group, etc.), sulfamoyl Groups (e.g., sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), sulfonamide groups (e.g., methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.), sulfo Luoxy group (for example, methanesulfonyloxy group), acyloxy group (for example, acetyloxy, benzoyloxy group, etc.), ureide group (for example, ureide, methylureide, ethylureide, phenylureide group, etc.), thioureide group (thioureide, methylthioureide group, etc.) ), An oxycarbonylamino group (eg, methoxycarbonylamino, phenoxycarbonylamino group, etc.), an oxysulfonyl group (eg, methoxysulfonyl group), and a phosphino group (eg, diphenylphosphino group).

As the heterocyclic group, for example, pyridyl, piperidino, morpholino, pyrazolyl, chenyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl,
Those substituted with each group such as thiadiazolyl and polyazaindenyl ring groups can be mentioned.

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

The telluro ether compound of the general formula [I] according to the present invention can be synthesized, for example, by the method of “Journal of Medicinal Chem”.
mistry) Vol 26.1293-1300 (1983) or "Inorganic Chemistry" V
ol can be easily obtained by referring to the method described in 18.2696 to 2700 (1979) or JP-A-2-118566.

Next, the compounds of the general formulas [II] and [III] according to the present invention will be described in detail.

In the formula, R ₁ and R ₂ represent * A ₁ -X _n A _2- , and are assumed to be bonded to a selenium atom at *. A ₁ and A ₂ each independently represent a linear or branched alkylene group (eg, methylene, ethylene, propylene, butylene, etc.), a cycloalkylene group (eg, a cyclohexylene group), an alkenylene group,
Represents an aralkylene group or an arylene group.

n is 0 to 3, and R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group,
A propyl group, an isopropyl group, etc.), a substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, etc.), a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, Etc.) or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

Y ₃ and Y _{4 in the} general formulas [II] and [III] each independently represent a hydroxy group, a carboxylic acid or a salt thereof (eg, an alkali metal salt,
Ammonium salts, etc.), sulfonic acids or salts thereof (eg, alkali metal salts, ammonium salts, etc.), and amino groups which may be substituted with an alkyl group or an aryl group (including salt forms. For example, unsubstituted amino groups, Dimethylamino group,
Dimethylamino hydrochloride, anilino group, etc.), ammonium group (eg, trimethylammonium chloride group, etc.), ether group (eg, methoxy group, ethoxy group, phenoxy group, etc.), thioether group (eg, methylthio group) Phenylthio group, etc.), selenoether group (eg, methylseleno group, ethylseleno group, 4-methylphenylseleno group, etc.), ureido group (eg, unsubstituted ureido group, 3-methylureido group, 3-phenylureido group) ), A thioureido group (eg, an unsubstituted thioureido group, a 3-methylthioureido group, etc.), an oxycarbonylamino group (eg, a methoxycarbonylamino group, a phenoxycarbonylamino group, etc.), an acyl group (eg, an acetyl group) , Benzoyl group, etc.), sulfonyl group (eg, methyl Sulfonyl group, etc.), a carbamoyl group (e.g., unsubstituted carbamoyl group, dimethylcarbamoyl group, etc.), a carbonamido group (e.g., formamide group, acetamide group, benzoyl amide group, etc.),
Sulfamoyl group (for example, unsubstituted sulfamoyl group,
Dimethylsulfamoyl group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (eg, Methanesulfonyloxy group, etc.), oxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), oxysulfonyl group (eg,
Methoxysulfonyl group, etc.), heterocyclic group (for example, morpholino group, piperidino group, 2-piperidyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 2-imidazolyl group, 2-tetrahydrofuryl group, A tetrahydrothienyl group, etc.).

R ₃ is a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, etc.),
A substituted or unsubstituted cycloalkyl group (eg, cyclohexyl group, cyclopentyl group, etc.), a substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, etc.), a substituted or unsubstituted alkenyl group ( For example, a propenyl group, a 1-methylvinyl group, etc.),
Or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

Hereinafter, specific examples of the compounds represented by the general formulas [II] and [III] of the present invention are shown, but the present invention is not limited thereto.

The organic selenoether compounds of the general formulas [II] and [III] according to the present invention described above include, for example, "The Chemistry of Organic Selenium and Tellurium"
Compounds "(The Chemistry of organic Selenium
and Tellurium Compounds) Vol-2. P495 (1987), JA
m.Chem.Soc. 60 .619 (1938), Anorg.Allg.Chem. 352 .295
(1967) and the like, or a synthetic method analogous thereto.

In the present invention, the above general formulas (I), (II) and (II)
The compound of the formula (I) may be used in the step of producing a silver halide emulsion, preferably during the time of precipitation of silver halide grains, during physical ripening or during chemical ripening, and particularly preferably during physical ripening.

The amount used is not uniform depending on the type of compound, emulsion conditions, etc., but may be used in a wide range of 0.001 to 100 g per mol of silver halide, and 0.003 to 30 g, preferably when used when forming silver halide grains. Is from 0.01 to 10 g.

When used at the time of chemical ripening, it may be 0.001 to 10 g, preferably 0.003 to 1 g.

In order to use the telluroether type compound or selenoether type compound according to the present invention, the compound may be dissolved in water or a hydrophilic solvent such as methanol and then added to the silver halide emulsion. If used, protective colloids such as gelatin or halide solutions,
It may be added in advance to a silver nitrate solution or the like.

The compounds of the general formulas (I), (II) and (III) according to the present invention may be used in combination with other sensitizers such as thioethers and thiocyanates such as rhodamonmon or ammonia. Good.

Next, the compound represented by the general formula [VI] will be described.

General formula (IV) In the formula, R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkenyl group, or Represents R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ¹ and R ² may combine with each other to form a ring.

M represents a hydrogen atom, an alkali metal atom or an ammonium group.

In the formula, the alkyl group represented by R is a linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. Group, i-butyl group, sec-butyl group, n
-Pentyl, t-pentyl, n-hexyl, cyclohexyl, octyl, dodecyl, octadecyl and the like.

Examples of the substituted alkyl group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, and the like among these alkyl groups having 1 to 8 carbon atoms.

Examples of the aryl group include a phenyl group and a naphthyl group which may be substituted with, for example, halogen, an alkyl group having 1 to 4 carbon atoms or an alkoxy group as a substituent.

Examples of the alkenyl group include an allyl group and a 2-butenyl group.

The alkyl group of R ¹ and R ^{2 in} the formula is an alkyl group having 1 to 16 carbon atoms, which may be linear, branched or cyclic, and represents, for example, the same group as R described above.

The substituted alkyl group represented by R ¹ and R ² has 1 carbon atom.
Substituted alkyl groups having the same substituents as R described above in the alkyl groups of Nos. 8 to 8 can be mentioned.

Examples of the aryl group include a phenyl group and a naphthyl group which may be substituted with, for example, halogen, an alkyl group having 1 to 4 carbon atoms or an alkoxy group as a substituent.

R ¹ and R ² may combine with each other to form, for example, a morpholine ring, a piperidine ring and the like.

M is a hydrogen atom, an alkali metal atom such as potassium or sodium, or an ammonium group.

The compound represented by the general formula [IV] used in the present invention may be used in an amount of 5 × 10 ^-6 mol to 6 mol / mol of silver halide in the emulsion.
It is advantageously used in a proportion of × 10 ^-3 mol, particularly preferably 1 × 10 ^-3 mol.
The effect of the present invention is favorably exhibited in the range of × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol.

The compound of the general formula [IV] of the present invention may be dissolved in a hydrophilic solvent such as methanol, ethanol or the like and directly added and dispersed in the emulsion.

The timing of addition may be at any time during the production process of the silver halide emulsion, but in a preferred embodiment, the compound of the general formula (IV) is added to any of the steps from the start to the end of chemical ripening of the emulsion. It is preferably added, more preferably immediately after the completion of chemical ripening.

When the compound of the formula [IV] is added to a layer other than the silver halide emulsion layer, it may be used in a hydrophilic colloid layer adjacent to the emulsion layer, for example, a protective layer, an intermediate layer, a filter layer, a development control layer and the like.

Preferred is a photosensitive silver halide emulsion layer containing the above general formula [I], [II] or [III].

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

1 represented by the above general formula [IV] used in the present invention.
The -phenyl-5-mercaptotetrazole derivative is a compound known as a fog inhibitor for a silver halide photographic emulsion, and can be easily synthesized by, for example, the method described in U.S. Pat. No. 3,376,310.

When the silver halide photographic light-sensitive material of the present invention obtained as described above is subjected to development processing after image exposure, the total processing time is from 20 seconds to less than 90 seconds. The total processing time means that after image exposure of the silver halide photographic light-sensitive material of the present invention, the silver halide photographic light-sensitive material is inserted into a roller which is a light-sensitive material insertion port of an automatic developing machine, then passed through a developing tank, a fixing tank, and a washing tank, and is dried at the outlet of the drying section. Time to reach the final roller.

The total processing time is 20 seconds or more and less than 90 seconds, more preferably 20 seconds to 90 seconds, and particularly preferably 50 seconds or less.

The processing temperature is 60 ° C or lower, preferably 20 to 45 ° C.

 An example of the breakdown of the total processing time is shown below.

Processing Step Processing Temperature (° C) Processing Time (seconds) Insertion-1.2 Development + Migration 35 14.6 Fixation + Migration 33 8.2 Rinse + Migration 25 7.2 Squeeze 40 5.7 Dry 45 8.1 Total-45.0 As a preferred embodiment of the present invention, halogen It is particularly preferable to add at least one compound of the general formula (I), (II) or (III) at any time from the time of physical ripening to the time of the desalting step at the time of precipitation of silver halide grains, Is to be added during physical ripening.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, but particularly high sensitivity is obtained. From the viewpoint, silver iodobromide is preferred.

The silver halide grains in the photographic emulsion are cubic, octahedral,
Even if they are all isotropically grown like a tetradecahedron, polyhedral crystal like a sphere, twins with plane defects, or a mixture or composite of them Good.
The size of these silver halide grains may be as large as 0.1 μm or less to 20 μm.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22-23
Page 1 Emulsion Preparation and type
s) and (RD) No. 18716 (November 1979), page 648.

A preferred embodiment of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse emulsion referred to here means that at least 95% of the particles by number or weight are measured by a conventional method, for example, when the average particle diameter is measured,
The silver halide grains are within ± 40%, preferably within ± 30% of the average grain size. The grain size distribution of silver halide is
Either a monodisperse having a narrow distribution or a polydisperse emulsion having a wide distribution may be used.

The crystal structure of the silver halide may be different from the silver halide composition inside and outside.

The emulsion according to a preferred embodiment of the present invention is a core / shell type monodisperse emulsion having a clear two-layer structure comprising a low iodine shell layer in a high iodine core portion.

The silver iodide content of the high iodide part of the present invention is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

Methods for producing such monodispersed emulsions are known, for example, J. Pho
t.Sic.12.242 to 251 (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, UK Patent
Nos. 1,413,748 and U.S. Pat. Nos. 3,574,628 and 3,655,394.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus is particularly preferable. As a method for obtaining a core / shell emulsion, for example, British Patent 1,027,146, US Patents 3,505,068 and 4,444,877
And JP-A-60-14331.

The silver halide emulsion used in the present invention may be tabular grains having an aspect ratio of 5 or more.

The advantages of such tabular grains include, for example, improvement in spectral sensitization efficiency, improvement in graininess and sharpness of an image, and the like, for example, British Patent 2,112,157, U.S. Patent 4,439,520,
Nos. 433,048, 4,414,310, and 4,434,226.

The above-mentioned emulsions are either emulsions of a surface latent image type in which a latent image is formed on the grain surface, an internal latent image type in which a latent image is formed inside the grain, and a type in which a latent image is formed on the surface and inside. Is also good.
These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or JP-A-63-15 / 1988
As a particularly preferable desalting method, a method using G3, G8, etc., as an example of an aggregated polymer agent described in No. 8644 is mentioned.

In the emulsion according to the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, the aforementioned RD No. 1764
3 (December 1978) and RD-18716 (November 1979). The following table shows the types and locations of the compounds shown in these two research disclosures.

Examples of the support that can be used in the light-sensitive material according to the present invention include, for example, pages 28 and RD-18716 of RD-17643 described above.
Those described in the left column on page 647 can be mentioned.

As a suitable support, a plastic film or the like may be used, and the surface of the support may be generally provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The emulsion according to the present invention can be coated on one side or both sides of the support thus treated.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of spherical seed emulsion) The A ₁ solution was stirred vigorously at 40 ° C., was added B ₁ and C ₁ solution by a double jet method at 30 seconds, it was carried out the production of nuclei. The pBr at this time was 1.09 to 1.15.

After 1 minute 30 seconds, was added in 5 minutes aging C ₁ in 20 seconds. During ripening, the KBr concentration was 0.071 mol / and the ammonia concentration was 0.63 mol /.

Thereafter, the pH was adjusted to 6.0, and desalting was performed by a usual method. When this seed emulsion was observed with an electron microscope, the average particle size was 0.
This was a monodisperse spherical emulsion having a size of 29 μm and a distribution width of 17%.
Next, this was grown by the following method.

The above seed emulsion and the following three kinds of solutions were prepared to prepare a silver halide emulsion mainly composed of tabular twins.

Solution B _{2 and} solution C ₂ were added to the solution A ₂ stirred vigorously at 65 ° C. by the double jet method in 112 minutes. During this time the pH was 5.8, pAg
Kept at 9.0 throughout. The rate of addition of B ₂ liquid and C ₂ solution was increased linearly such that 6.4 times the initial and final.

After the addition was completed, the pH was adjusted to 6.0. Observation of the obtained emulsion under an electron microscope revealed tabular silver halide grains having an average grain size of 1.6 μm and a distribution of 19%. The average particle diameter / particle thickness of the particles was an average particle of 4.9. To the reaction solution after the completion of the physical ripening, exemplified compounds of the general formulas [I], [II] and [III] of the present invention were added as shown in Table 1.

The emulsion thus obtained was desalted again, and then subjected to chemical sensitization and spectral sensitization.

That is, after performing a gold / sulfur sensitization method using ammonium thiocyanate, chloroauric acid and sodium thiosulfate, 4-hydroxy-6-methyl1.3,3a, 7-tetrazaindene is added as a stabilizer, and then an appropriate amount of KI is added. And the following spectral sensitizing dyes were added at 300 mg and 5 mg / mol AgX, respectively.

To the obtained emulsion after chemical ripening, 29 types of emulsions were prepared by adding the exemplified compounds of the general formula [IV] according to the present invention shown in Table 1 and the following additives to prepare emulsion coating solutions.

On each emulsion layer, the following gelatin solution was prepared as a protective layer to prepare a coating solution for the protective layer.

The two coating solutions obtained were coated on both sides of a subbed polyester film support so that the emulsion layer had a silver content of 4.5 g / m ² and the gelatin was 3.1 g / m ² , and the protective layer had a gelatin content of 3.1 g / m ^2. There was a two-layer simultaneous coating per minute 100m so as to be 1.0 g / m ^2, to obtain a silver halide photographic light-sensitive material and dried.

The following additives are added to each emulsion layer per mole of silver halide.

The following compounds were added to the protective layer per 1 g of gelatin.

[Sensitometry] The sample thus obtained was used as a light source with the standard light B described in “New Edition, Data Book of Illumination”, ed. The film was exposed to the same light amount on both sides of the film at 3.2 cms with a non-filter.

The above sample is an SRX-501 automatic processor (made by Konica Corporation)
Using a developing solution and a fixing solution shown on the next page in a 45-second processing mode, the sensitivity of each sample was determined. The sensitivity was calculated by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0.
The relative sensitivity was defined assuming that the sensitivity of Sample 1 was 100.

Further, regarding the contrast, the obtained samples were visually compared, and the difference in contrast was evaluated on a scale of 1 (poor) to 5 (excellent) and shown in Table 1.

 Next, the compositions of the developing solution and the fixing solution used in the present invention are shown.

And pH 10.50 (25
° C).

Glacial acetic acid was added to the aqueous solution of No. 1 to obtain a solution having a pH of 4.0 (25 ° C.).

Both the developing solution and the fixing solution were processed by an automatic developing machine 24 hours after the preparation.

At that time, the pH of the developer was 10.34 (25 ° C) and the pH of the fixer was
4.08 (25 ° C).

The development processing tank temperature was 32.0 ° C. and the fixing processing tank temperature was 33.0 ° C.

In addition, the obtained sample was treated at 60 ° C and 50% relative humidity for 3 hours.
After standing for a day, the same exposure and development treatments were performed, and the increase in fog was measured. (Oven test) Further, through an incandescent lamp light through a red filter having a transmittance shown in FIG.
The increase in fog when irradiated from 1.2 m above the sample for 30 minutes was measured. Table 1 also shows these results.

<Comparative compound> (a) 3,6-dithia-1,8-octanediol (US Patent No. 30
(B) Tributyl tellurium iodide (JP-A-53-57)
No. 817) (C) 1-phenyl-5-mercaptotetrazole From the results shown in Table 1, the samples according to the present invention were halogenated without rapid reduction in sensitivity, without deterioration in sensitivity, excellent in photographic performance such as contrast and fogging, and also excellent in safelight property and heat fogging property. A silver photographic light-sensitive material can be obtained. Also, although the amount changes from No.24 to No.26,
It can be seen that around 50 mg / AgX is good.

[Effects of the Invention] According to the present invention, a silver halide light-sensitive material having excellent photographic performance even in rapid development processing, less generation of fog by safelight, and excellent stability over time is obtained.

[Brief description of the drawings]

FIG. 1 shows the transmittance of the red filter used in the embodiment of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/09 G03C 1/34

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on at least one side of a support, wherein the silver halide emulsion layer contains the following general formulas [I] and [II]. Or at least one compound represented by the general formula [IV] in the silver halide photographic light-sensitive material constituting layer. A silver halide photographic light-sensitive material comprising: In the general formula (I) Y ₁ -Te-Y ₂ formula, Y _1, Y ₂ may represent the same or different and may be substituted or unsubstituted aliphatic group, at least one of which, hydroxy group, amino group , Ammonium group, ether group, thioether group, selenoether group, mercapto group, carbamoyl group, carboxamide group, sulfonyl group, sulfamoyl group, sulfonamide group, sulfonyloxy group, acyloxy group, ureido group, thioureido group, thioamide group, Oxysulfonyl group, oxycarbonylamino group, sulfonic acid or a salt thereof, sulfinic acid or a salt thereof,
Phosphoric acid or a salt thereof, a phosphate group, a phosphino group,
Or a group substituted with a heterocyclic group. Formula II _{Y 3 -R 1 -Se-R 2} -Y 4 in the general formula (III) Y ₃ -R ₁ -Se-R ₃ formula, R _1, R ₂ are each independently a carbon atom, a nitrogen atom , An oxygen atom, a sulfur atom, and a selenium atom, and represents a divalent group, and R ₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. Y ₃ and Y ₄ are each a hydroxy group, an amino group, an ammonium group, an ether group, a thioether group, a selenoether group,
Carbamoyl group, carbonamido group, sulfonyl group, sulfamoyl group, sulfamido group, sulfonyloxy group, acyl group, acyloxy group, ureido group, thioureido group, oxysulfonyl group, oxycarbonyl group, oxycarbonylamino group, sulfone group, sulfonic acid Or a salt thereof, a carboxylic acid or a salt thereof, or a heterocyclic group. General formula (IV) In the formula, R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkenyl group, or Represents R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ¹ and R ² may combine with each other to form a ring. M represents a hydrogen atom, an alkali metal atom or an ammonium group.