JPH06266037A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain ultrahigh contrast, high sensitivity, low fog, and superior storage stability against the time lapse by chemically stabilizing a silver halide emulsion in the presence of a polysulfide compound and spectrally sensitizing it with a specified sensitizing dye. CONSTITUTION:The silver halide emulsion is chemically sensitized in the presence of the polysulfide compound and spectrally sensitized with at least one of the sensitizing dye represented by formulae I and/or II in which R1 is alkyl: Z is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; is a nonmetallic atomic group necessary to form a 5-membered hetero ring; m is 1 or 2: Z is a nonmetallic atomic group necessary to form an oxazole or benzoxazole ring or the like; R1 in formula II is an optionally substituted alkyl; R2 in formula II is an alkoxycarbonylalkyl, hydroxyalkyl, or the like; and each of R3 and R4 is, independently, H, alkyl, or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a superhigh-contrast silver halide photographic light-sensitive material having excellent stability over time.

[0002]

2. Description of the Related Art In order to sufficiently cope with remarkable improvement in quality in the field of printing and plate making, there is a demand for higher contrast and higher sensitivity, and further improvement in graininess, fog, developability, storability and the like. In particular, in recent years, development speed has been improved and higher sensitivity has been required due to demands such as the use of a light source that has a low output but is inexpensive, and a reduction in working time.

However, in the technique of increasing the sensitivity, for example, making emulsion grains larger or increasing the silver bromide ratio generally causes a softening tone and tends to deteriorate the storability. Recently, a technique of increasing the contrast without relying on lith development by using a so-called contrast-increasing agent such as a tetrazolium compound or a hydrazine derivative has been used, but in this case, the performance tends to change with time. In addition, in the technology of sensitizing sulfur with hypo, thiourea, and using the above-mentioned sulfur sensitizers together with precious metals such as gold, the sensitivity of fog is generally increased, the storage stability is deteriorated, and the fog density is reduced to a desired level. If this is done, there is a problem in that the sensitivity is greatly reduced.

[0004]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which has super-high contrast, high sensitivity, low fog and excellent stability over time. It is in.

[0005]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion is a polysulfide compound. Chemically sensitized in the presence of the compound of the general formula [1] (Chemical formula 1) and / or the general formula [2]
This is achieved by a silver halide photographic light-sensitive material characterized by being spectrally sensitized with at least one sensitizing dye represented by (Chemical Formula 2).

The silver halide photographic light-sensitive material of the present invention preferably contains a tetrazolium compound (Chemical Formula 3).

A more specific description will be given below.

First, the polysulfide compound according to the present invention will be described.

The polysulfide compound in the present invention is 3
Organic and inorganic compounds having one or more sites in which one or more sulfur atoms are linked. As the polysulfide compound, a linear, branched or cyclic compound may be used, but a compound having a cyclic polysulfide group is particularly preferable from the viewpoint of stability of the polysulfide compound. Specific examples of these compounds include the following compounds. Of course, the present invention is not limited to this.

[0010]

[Chemical 4]

Regarding the timing of adding the polysulfide compound, it can be added in any step as long as it is in the state of being chemically sensitized in the presence of the polysulfide compound. Specifically, chemical sensitization is performed before the formation of silver halide grains, during the formation of silver halide grains, from the end of silver halide grain formation to the desalting step, and from the desalting step to the start of chemical sensitization. It may be at any time selected from the start of sensation and during chemical sensitization. Preferably, from the end of silver halide grain formation to before the desalting step, from the desalting step to the start of chemical sensitization, at the start of chemical sensitization and during chemical sensitization. Of these, particularly good is the initiation of chemical sensitization.

The amount of the polysulfide compound added varies depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect, but is 1 × 1 per mol of silver halide.
0 is ^{-5 mg~100mg.} It is preferably 1 × 10 ^{−3 to} 10 mg.

Next, the compound represented by the general formula [1] (Formula 1) will be described.

In the general formula [1], R ₁ is an alkyl group, specifically, for example, an alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2- Acetoxyethyl group, carboxymethyl group, 2-
Carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, n-propyl group, Isopropyl group, n-butyl group and the like are preferable. Z is a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle, and the heterocycle includes, for example, a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring, Benzoxazole ring, naphthothiazole ring, naphthoselenazole ring, naphthoxazole ring, viridine ring, quinoline ring and the like,
Further, these heterocycles may have a substituent, and these substituents are, for example, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), for example, an alkyl group, preferably having 1 to 1 carbon atoms.
4 alkyl groups (eg, methyl group, ethyl group, n-propyl group, etc.), halogenated alkyl groups (eg, trifluoromethyl group, etc.), alkoxy groups, preferably 1 to 1 carbon atoms
4 alkoxy groups (eg methoxy, ethoxy, n-
Propyloxy group etc.), hydroxy group, aryl group (eg phenyl group etc.) and the like. Q ₁ represents a group of non-metal atoms necessary for forming a 5-membered heterocycle, and examples of the heterocycle include a rhodanine ring, a thiohydantoin ring, a thiooxazolidinedione ring and a thioselenazolidinedione ring. These heterocycles may have a substituent, and these substituents are alkyl groups, preferably alkyl groups having 1 to 8 carbon atoms (for example, methyl group, ethyl group, n-propyl group, 2 -Hydroxyethyl group,
2-hydroxyethyloxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfo Propyl group, 3-sulfobutyl group, 4-sulfobutyl group, benzyl group, phenethyl group, n-propyl group, n-butyl group, etc.), aryl group (eg phenyl group, p-sulfophenyl group etc.), pyridyl group (eg 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4-methyl-2-pyridyl group and the like). Further, m represents 1 or 2.

Examples of the compound represented by the general formula [1] used in the present invention include the following 1-1 to 1-25.

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

The compound represented by the above general formula [1] used in the present invention can be easily synthesized based on the method described in, for example, US Pat. No. 2,161,331 and West German Patent 936,071. . The above general formula [1]
To use the compound represented by in a silver halide emulsion,
It may be added and dissolved in the coating liquid, or may be dissolved in water or an organic solvent such as methanol, ethanol, acetone or the like or a mixture thereof and added to the coating liquid at an arbitrary time. Usually, it may be added at any time from the end of aging to just before coating. It is preferably added to the silver halide emulsion layer. However, if necessary, it can be added to a layer adjacent to the silver halide emulsion layer, for example, a protective layer or an intermediate layer as long as it does not affect the photographic performance.

The amount of the compound represented by the above-mentioned general formula [1] used in the present invention when it is added to a silver halide emulsion varies depending on the kind of silver halide emulsion and the kind of compound. 1 per mole of silver halide
The amount is in the range of mg to 2 g, more preferably 10 mg to 1 g, and the optimum amount for obtaining the effect can be arbitrarily selected.

Next, the general formula [2] will be described.

In the formula, Z represents an atomic group necessary for completing an oxazole nucleus, a benzoxazole nucleus or a naphthoxazole nucleus, and these nuclei may have a substituent on a carbon atom. Specific examples of the substituent include a halogen atom (eg, fluorine atom, chloro atom, prom atom) and an unsubstituted alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) , An alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group), a hydroxy group, an alkoxycarbonyl group having 2 to 6 carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), carbon number 2-5
And an alkylcarbonyloxy group (eg, acetyloxy group, propionyloxy group, etc.), phenyl group, hydroxyphenyl group and the like.

Specific examples of these nuclei include oxazole, 4-methyloxazole and 5-
Methyloxazole, 4,5-dimethyloxazole, 4-
Phenyloxazole, etc .; Benzoxazole as nucleus, benzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxy Carbonylbenzoxazole, 5-
Acetyloxybenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 6-methoxybenzole, 5,6-dimethylbenzoxazole, 6-chloro-5-methylbenzoxazole, etc. Cores such as -d] oxazole, naphtho [2,1-d] oxazole, and naphtho [2,3-d] oxazole can be cited.

R ₁ represents an unsubstituted or substituted alkyl group. Examples of the substituent include a hydroxy group, a sulfonate group, a carboxyl group, a halogen atom (for example, a fluorine atom and a chlorine atom), an unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (an alkoxy group is a sulfo group or a hydroxy group. Optionally substituted), an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms,
Sulfamoyl group, unsubstituted or substituted carbamoyl group (including a substituted carbamoyl group substituted by an alkyl group having 1 to 4 carbon atoms), a substituted phenyl group (examples of the substituent are a sulfo group, a carboxy group, a hydroxy group, etc.) , Vinyl groups and the like.

Specific examples of the unsubstituted alkyl group include methyl group, ethyl group, propyl group and butyl group.
Examples of the substituted alkyl group are 2-hydroxyethyl group and 3-hydroxypropyl group as hydroxyalkyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group and 2 as sulfoalkyl group. -Hydroxy-3-sulfopropyl group, 2-chloro-3-sulfopropyl group, 2-sulfonate ethyl group, 3-sulfonate propyl group, carboxyalkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, etc. 2,2,2-trifluoroethyl group, 2- (3-sulfopropyloxy) ethyl group, 2- (2-
Phenethyl group such as (hydroxyethoxy) ethyl group, ethoxycarbonylethyl group, methylsulfonylethyl group, 2-sulfamoylethyl group as sulfamoylalkyl group, 2-carbamoylethyl group, 2-N, N-dimethylcarbamoylethyl group , P-carboxyphenethyl group,
P-sulfophenethyl group as a sulfoaralkyl group, o-
Examples thereof include sulfophenethyl group, p-hydroxyphenethyl group, phenoxyethyl group and the like. R ₂ is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl group, or a substituent (CH ₂ ) n A or (CH ₂ ) represents a _{n O (CH 2) n a} . Here, A is a nitrile group, an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamino group, or a carbon number of 1.
~ 8 represents an alkoxy group, and n represents an integer value of 1 to 4.

The above-mentioned groups represented by R ₂ include those having a substituent. For example, those in which the alkyl portion of the above group is substituted with a halogen atom can also be preferably used.

Examples of R ₂ are an alkoxycarbonylalkyl group in which an alkyl group is substituted with a halogen atom (eg, methoxycarbonylfluoromethyl group, ethoxycarbonylfluoromethyl group, fluoroethoxycarbonylethyl group, etc.), hydroxyalkyl group ( For example
2-hydroxyfluoroethyl group, 2-hydroxyfluoropropyl group, 3-hydroxyfluoropropyl group, 2,3
-Dihydroxyfluoropropyl group, etc., hydroxyalkoxyalkyl group (eg hydroxymethoxyfluoromethyl group, 2- (2-hydroxyfluoroethoxy) ethyl group, 2-hydroxyfluoroethoxymethyl group, etc.), carbamoylalkyl group (N-alkyl substitution) , N, N-dialkyl substituted, N-hydroxyalkyl substituted, N-alkyl-
Includes N-hydroxyalkyl-substituted, N, N-di (hydroxyalkyl) -substituted carbamoylalkyl groups and carbamoylalkyl groups of 5- or 6-membered cyclic amines (eg 2-carbamoylchloroethyl group, 2-N- (2-hydroxyethyl) carbamoylchloroethyl group, N-hydroxyfluoroethylcarbamoylmethyl group, N, N-di (2
-Hydroxyfluoroethyl) carbamoylmethyl group, 2
-N, N-di (2-hydroxyethyl) carbamoylchloroethyl group, N, N-dimethylcarbamoylchloromethyl group, morpholinocarbamoylchloromethyl group, piperidinocarbamoylmethyl group, etc.), hydroxyphenyl group, carbon number 7- A hydroxyalkylphenyl group of 9 (eg p- (2-
Hydroxyfluoroethyl) phenyl group, m- (1-hydroxyfluoroethyl) phenyl group, etc.) or substituent
Represents (CH ₂ ) n A or (CH ₂ ) n O (CH ₂ ) n A. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamino group, or a lower alkoxy group, and the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (for example, methyl group). Sulfonyl group, ethylsulfonyl group, etc.),
The sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms (for example, N-methylsulfonamide group, N, N
-Dimethylsulfonamide group etc.), an alkylsulfonylamide group etc.), the alkylsulfonylamino group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms (for example, a methylsulfonylamino group), The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.). n represents an integer value of 1 to 4.

R ₃ and R ₄ may be the same or different,
Each is a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 4, such as a methyl group, an ethyl group, etc.), an alkoxy group (preferably having a carbon number of 1 to 4, such as a methoxy group,
Ethoxy group, etc.), alkylsulfonyl group, sulfo group,
Represents a chlorine atom, a fluorine atom or a carboxyl group. In the compound represented by the above general formula [2], particularly preferred is when R ₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a sulfo group or a carboxyl group and / or a hydroxyl group. And specifically include sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3-sulfo-2-hydroxypropyl group and the like.

Next, the above general formula [2] used in the present invention is used.
Typical examples of the compound represented by are shown below, but it goes without saying that the compound used in the present invention is not limited to these.

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

The compound represented by the above general formula [2] used in the present invention is, for example, Japanese Patent Publication Nos. 46-549 and 46-18.
No. 105, No. 46-18106, No. 46-18108, No. 47-4085, No. 5
8-52574, U.S. Patents 2,839,403, 3,384,486, 3,6
25,698, 3,480,439, 3,567,458 and the like can be synthesized according to the method for synthesizing dimethine merocyanine. The merocyanine dye represented by the above general formula [2] used in the present invention can be added and dispersed in a silver halide emulsion by a conventionally known method. For example, JP-B-49-44895, a method of dispersing and adding together with the surfactant described in JP-A-50-11419,
JP-A-53-16624, 53-102732, 53-102733, U.S. Pat.Nos. 3,469,987, 3,676,147, a method of adding as a dispersion with a hydrophilic substrate, East German Patent No.
Examples include the method of adding as a solid solution described in the specification of No. 143,324. Other merocyanine dyes with water-soluble solvents such as water, ethanol, methanol, acetone, n-
It may be added to the emulsion by dissolving it in propanol, fluorinated alcohol, pyridine or the like alone or in a mixed solvent thereof. The time of addition may be at any time during the emulsion production process, but is preferably during or after chemical ripening. The addition amount of the merocyanine dye used in the present invention is an amount for spectrally sensitizing a silver halide emulsion, for example, 1 mg to 2 g, preferably 10 mg to 1 g per mol of silver halide.

The merocyanine dyes used in the present invention are, for example, Japanese Patent Publication Nos. 43-4933, 43-4936 and 46-181.
07, 46-1999, 47-11114, 48-1762, 48
-1762, 48-38408, 56-38937, 58-52574,
Supersensitization can be achieved by using it in combination with other dyes disclosed in the specifications of US Pat. Nos. 2,519,001 and 3,745,014 in an arbitrary amount ratio.

In the present invention, the substituents R ₁ , R ₂ and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [3] are hydrogen atoms or Hammett's sigma value (σP) showing electron withdrawing degree. Is preferably negative or positive. Particularly negative ones are preferable.

Hammett's sigma values for phenyl substitution are well documented, eg, Journal of Medical Chemistry, Volume 20,
See page 304, 1977, C. Hansch, etc., and particularly preferable groups having a negative sigma value include, for example, a methyl group (σP = -0.17 or less). σP value) ethyl group (-0.15), cyclopropyl group (-
0.21), n-propyl group (-0.13), isopropyl group (-0.1
5), cyclobutyl group (-0.15), n-butyl group (-0.16), is
o-butyl group (-0.20), n-pentyl group (-0.15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group ( -
0.27), ethoxy group (-0.24), propoxy group (-0.25),
Examples thereof include a butoxy group (-0.32), a pentoxy group (-0.34) and the like, all of which are useful as a substituent of the compound of the general formula [3] of the present invention.

Specific examples of the compound of the general formula [3] used in the present invention will be given below, but the compound of the present invention is not limited thereto.

[0047]

[Table 1]

The tetrazolium compound used in the present invention is, for example, a chemical review compound.
It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound of the present invention is contained in the silver halide photographic light-sensitive material of the present invention in an amount of from about 1 mg to about 10 g, preferably about 10 mg, per mol of silver halide.
It is preferably used in the above range of about 1 g.

The silver halide photographic light-sensitive material of the present invention comprises a support and at least one silver halide emulsion layer and at least one hydrophilic colloid layer coated on the support. Is coated directly on the support or through a hydrophilic colloid layer containing no silver halide emulsion, and the hydrophilic colloid layer is provided on the silver halide emulsion layer or on the support and halogen. It may be coated as a protective layer between silver halide emulsion layers. Further, the silver halide emulsion layer may be divided into silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, the silver halide emulsion layer may have an intermediate layer of the hydrophilic colloid layer between the layers, or an intermediate layer between the silver halide emulsion layer and the protective layer. Good. The layer containing the tetrazolium compound of the present invention is a silver halide emulsion layer and / or various hydrophilic colloid layers described above.

The most preferred embodiment of the present invention is that the tetrazolium compound of the present invention is contained in the silver halide emulsion layer, and the hydrophilic colloid contained in the silver halide emulsion layer and the hydrophilic colloid layer is gelatin or a gelatin derivative. Which is a silver halide photographic light-sensitive material.

In order to incorporate the tetrazolium compound of the present invention into the silver halide emulsion layer and / or the hydrophilic colloid layer, the tetrazolium compound may be dissolved in appropriate water and an organic solvent and added, or it may be dissolved in an organic solvent. Examples thereof include a method in which the liquid is dispersed in a hydrophilic colloid matrix such as gelatin or a gelatin derivative and then added, or a method in which the liquid is dispersed and added. The present invention may use any of these methods.

The tetrazolium compound used in the present invention can be used alone to obtain preferable image characteristics. Further, this tetrazolium compound does not adversely affect the image characteristics even if two or more kinds thereof are used in combination at an appropriate ratio. Further, the tetrazolium compound of the present invention and the tetrazolium compound other than the present invention may be used in an appropriate ratio.

In a preferred embodiment of the present invention,
The tetrazolium compound according to the present invention may be added to the silver halide emulsion layer. In another preferred embodiment of the present invention, a hydrophilic colloid layer directly adjacent to a hydrophilic colloid layer containing a silver halide emulsion layer,
Alternatively, it is added to the adjacent hydrophilic colloid layer via the intermediate layer.

In another embodiment, the tetrazolium compound according to the present invention is dissolved in a suitable organic solvent, for example, alcohols such as methanol and ethanol, ethers, esters, etc., and silver halide photography is carried out by an overcoat method or the like. It may be incorporated in the silver halide photographic light-sensitive material by directly coating it on the portion of the light-sensitive material which will be the outermost layer on the silver halide emulsion layer side.

In the present invention, particularly preferable results can be obtained by using an anion which is combined with the tetrazolium compound of the present invention and reduces the hydrophilicity of the tetrazolium compound of the present invention. Examples of such anions include acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically lower alkylbenzene such as p-toluenesulfonic acid anion. Sulfonate anions, p-dodecylbenzene sulfonate anions, alkylnaphthalene sulfonate anions, lauryl sulfate anions, tetraphenylborones, di-2-ethylhexyl sulfosuccinate anions and other dialkyl sulfosuccinate anions, Examples thereof include polyether alcohol sulfate anion such as cetyl polyethenoxysulfate anion, stearic acid anion, and polyacrylic acid anion.

Such anions may be added to the hydrophilic colloid layer after being pre-mixed with the tetrazolium compound of the present invention, or they may be contained alone or without the tetrazolium of the present invention in the silver halide emulsion layer. Alternatively, it can be added to the hydrophilic colloid layer.

In the chemical sensitization in the present invention, gold,
It is particularly preferable to use a sensitizer with a precious metal such as platinum in combination. Examples of these noble metal sensitizers include gold sensitizers (US Pat. Nos. 2540085, 2597876, and 2399).
Sensitization with Group VIII metal ion compounds,
(U.S. Patent Nos. 2448060, 2540086, 2566245
No. 2566263, No. 2598079, etc.). In addition, in the present invention, a reduction sensitizer (US Patent No.
No. 2518698, No. 2419974, No. 2983610, etc.) are also applicable.

The silver halide emulsion used in the present invention (hereinafter referred to as a silver halide emulsion or simply an emulsion) contains, for example, silver chloride in an amount of 50 mol% or more, as silver halide.
A silver chlorobromide emulsion or a silver chloroiodobromide emulsion containing 55 to 90 mol% is preferably used, but a monodisperse emulsion having a monodispersity degree of 20 or less and a grain size of 3 μm or less, particularly 0.1 to 1
μm is preferred. As the definition of monodispersity, the definition described in JP-A-62-32444 was used.

In the emulsion of the present invention, 10 ^-5 to 10 ^-10 mol, preferably 10 ^-6 mol, per mol of silver halide, are used by the end of grain formation.
It is preferable that the rhodium salt (containing complex salt) is contained in an amount of ˜10 ⁻⁹ mol. As such a rhodium salt, any conventionally known one can be arbitrarily used, and is typically [Na ₃ RhC
l ₆ ], [K ₃ RhBr ₆ ], rhodium chloride ammine complex, rhodium trichloride, etc. are used.

In addition to the rhodium salt, the emulsion of the present invention is selected from cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salt containing) and iron salt (complex salt containing) by the end of grain formation. At least one of

The silver halide is generally desalted after the physical ripening in order to remove unnecessary salts. As the desalting method, any method such as gelation, dialysis, salting out with water-soluble sulfate, etc. can be used. In the gelation method using a modified gelatin or an acrylic acid-based polymer, The use of the desalting method and the sensitizing method of the present invention is preferable from the viewpoint that the effect of suppressing fog is particularly large.

Examples of the modified gelatin include Japanese Patent Application No.
Examples thereof include the compounds described in No. 3-324968.

As the acrylic acid-based polymer,
For example, JP-B-47-17854, JP-A-52-67318, JP-A-3-
Examples thereof include the compounds described in No. 288143.

The silver halide photographic light-sensitive material of the present invention can have a hydrophilic colloid layer in addition to at least one silver halide emulsion layer. Further, at least one hydrophilic colloid layer can be provided on the opposite side of the support from the silver halide emulsion layer. Examples of hydrophilic colloids contained in the silver halide emulsion layer and hydrophilic colloid layer include gelatin (either coal-treated or acid-treated), gelatin derivatives, polymer graft compounds of gelatin, and synthetic hydrophilic polymer compounds. However, gelatin is preferred in the silver halide photographic light-sensitive material of the present invention.

The silver halide photographic light-sensitive material of the present invention is described as a hydrazine compound as described in JP-A-56-106244, which is known as a contrast enhancer, and in JP-A-57-132137. The tetrazolium compound which exists can be used.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention.

For example, in the silver halide photographic emulsion and other hydrophilic colloid layers used in the present invention, various chemical sensitizers, color tones, hardeners, surfactants, thickeners, A plasticizer, a slip agent, a development inhibitor, an ultraviolet absorber, an anti-irradiation dye, a heavy metal matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion of the present invention and other hydrophilic colloid layers.

These additives are described in more detail in Research Disclosure Vol. 176, Item 17643 (December 1978) and Vol. 187, Item 18716 (November 1979). As a support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polyethylene, baryta paper, paper coated with polyolefin, glass , Metals and the like. These supports are subjected to a surface treatment if necessary.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by various methods such as a commonly used method after exposure.

[0071]

【Example】

Example 1 A silver chlorobromide emulsion was prepared using solutions A, B, and C shown below. [Solution A] 17 g of ossein gelatin Polyisopropylene-polyethyleneoxy disuccinate sodium salt 10% aqueous solution of ethanol 5 ml distilled water 1280 ml [Solution B] 170 g of silver nitrate distilled water 410 ml [Solution C] sodium chloride 45.0 g potassium bromide 27.4 g Rhodium chloride trihydrate 28 μg Polyisopropyleneoxydisuccinate sodium salt 10% Ethanol solution 3 ml Ocein gelatin 11 g Distilled water 407 ml After keeping solution A at 40 ° C, sodium chloride was added so that the EAg value was 160 mV. .

Next, Solution B and Solution C were added by the double jet method using the mixing stirrers described in JP-A-57-92523 and JP-A-57-92524.

As shown in Table 1, the addition flow rate was 80 at the total addition time.
The addition flow rate was gradually increased over a period of minutes, and the addition was performed while keeping the EAg value constant.

The EAg value was 160 mV, and 3 ml / 5 minutes after the start of addition.
The EAg value was changed to 120 mV with 1 l of aqueous sodium chloride solution, and this value was maintained thereafter until the mixing was completed. In order to keep the EAg value constant, the EAg value was controlled using a 3 mol / l sodium chloride aqueous solution.

For the measurement of the EAg value, a metallic silver electrode and a double junction type saturated Ag / AgCl reference electrode were used (the double junction disclosed in JP-A-57-197534 was used for the electrode construction). ).

For addition of solutions B and C, a variable flow rate roller tube metering pump was used.

During the addition, sampling of the emulsion gives
It is confirmed by observing with an electron microscope that no new particles are generated in the system.

During the addition, the pH value of the system was controlled with a 3% nitric acid aqueous solution so as to keep the pH value constant at 3.0. After the addition of solutions B and C, the emulsion was ripened for 10 minutes in Ostwald, then desalted and washed in a conventional manner, and then an aqueous solution of ossein gelatin was used.
Add 600 ml (containing 30 g of ossein gelatin), 55 ℃ ・ 30
After dispersing by stirring for 1 minute, the volume was adjusted to 750 ml.

Next, these emulsions were adjusted to pH 5.8 and pAg 7.0 with citric acid and sodium chloride, and then chloroauric acid was added at 2 × 10 ^-5 mol per mol of silver and sulfur sensitizer (Table 2) per 1 mol of silver and 7 mg of sodium thiosulfate as a comparative compound were added, and the mixture was chemically ripened at 60 ° C. for 120 minutes to reach the maximum sensitivity. Then 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added to 60 mg and 600 mg, respectively, per mol of silver.
Addition stopped aging. The emulsion thus obtained was divided and a sensitizing dye was added.

Sodium n-dodecylbenzel sulfonate
600 mg / Ag 1 mol, styrene-maleic acid copolymer 2 g /
1 mol of Ag was added, and 3.5 g of Ag and 2.0 g / m ^{2 of} gelatin were coated on a polyethylene terephthalate film. At that time, 1-decyl-2- (3-isobentyl) succinate 2-sodium sulfonate is used as a spreading agent at 30 mg / m ^{2 so} that the amount of gelatin becomes 1.0 g / m ^2, and formalin 25 mg / as a hardening agent.
A dural protective layer containing m ² was applied in multiple layers.

The obtained sample was divided into two parts, and half was left as it was.
One half was left under high temperature and high humidity at a temperature of 40 ° C. and a relative temperature of 80% for 3 days, and then exposed with a tungsten light source using a wedge.

The exposed sample was processed in an automatic developing machine using a developing solution and a fixing solution having the following formulations.

[0083] <Developer formulation> (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to make the pH of the used solution 10.4 Potassium bromide 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) ) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 700 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was made up to 1 liter.

<Fixer Formulation> (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% w / v Aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% w / v aqueous solution) 4.7 g Aluminum sulfate (aqueous solution with an Al ₂ O ₃ equivalent content of 8.1 w / v) 26.5 g Fixer At the time of use, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was made up to 1 liter and used. The pH of this fixer is approximately
It was 4.3.

The photographic characteristics of the samples obtained after processing are shown in Table 3. In addition, gamma is shown by the amount logE value of the linear portion from the optical density of 0.2 to 1.5, and is a relative value when 100 is taken for 3 days of natural standing of sample No. 1.

For the fog, the density of the unexposed film at that time was measured.

The results are shown in Table 2.

[0088]

[Chemical 20]

[0089]

[Table 2]

From the results shown in Table 2, it can be seen that the samples of the present invention have excellent sensitivity and fog, and also have excellent stability with time.

Example 2 A tetrazolium compound 3-4 was added to each emulsion at the time of emulsion preparation.
Same as Example 1 except that 0 mg / Ag 1 mol was added.

The results are shown in Table 3.

[0093]

[Table 3]

From the results shown in Table 3, it can be seen that the sample of the present invention is excellent in photographic performance and temporal stability as in the case of Example 1, even when a contrast-increasing agent such as a tetrazolium compound is added.

[0095]

According to the present invention, ultra-high contrast and high sensitivity,
It was possible to provide a silver halide photographic light-sensitive material having low fog and excellent stability over time.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, said silver halide emulsion being chemically sensitized in the presence of a polysulfide compound, and having a general formula A silver halide photographic light-sensitive material, which is spectrally sensitized with at least one sensitizing dye represented by [1] and / or general formula [2]. [Chemical 1] [Wherein R ₁ is an alkyl group, Z is a non-metal atom group necessary for forming a 5- or 6-membered heterocycle, and Q ₁ is a non-metal atom necessary for forming a 5-membered heterocycle. Represents an atomic group, m
Represents 1 or 2. ] [Chemical 2] [In the formula, Z represents a nonmetallic atom group necessary for forming an oxazole nucleus, a benzoxazole nucleus, or a naphthoxazole nucleus. R ₁ represents an unsubstituted or substituted alkyl group. R ₂ represents an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, or (CH ₂ ) n A. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamino group, or a lower alkoxy group, and n represents an integer value of 1 to 4. R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a chlorine atom or a carboxyl group. ] 2. The silver halide photographic light-sensitive material according to claim 1, containing a compound represented by the general formula [3]. [Chemical 3] [Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a group showing a negative value of Hammett's sigma value (σ _p ) ga,
X ^- represents an anion. However, R ₁ , R ₂ and R ₃ are not hydrogen atoms at the same time. ]