JPH0748102B2 - Spectrally sensitized silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material spectrally sensitized by a novel merocyanine dye, and in particular, a halftone image having high green light sensitivity and high contrast. The present invention relates to a silver halide photographic light-sensitive material which can be obtained even in a relatively quick phenomenon and has little dye contamination after processing.

[Conventional technology]

It is known that silver halide light-sensitive materials can be used to form photographic images with extremely high contrast. For example, the average grain size of silver halide grains is about 0.5 μm.
The following fine grains have a narrow grain size distribution, uniform grain shape, and a high silver chloride content of, for example, 50 mol% or more. A silver halide sensitized silver halide or silver chloroiodide emulsion. There is known a method of obtaining a high-contrast halftone image or line image by treating a material with an alkaline developing solution having a low sulfite ion concentration and containing only hydroquinone as a developing agent.

This type of silver halide light-sensitive material is known as a lith-type silver halide photographic light-sensitive material, and usually has a large and small area proportional to the density change in continuous tone of an original in the photolithography process. It is used to convert to a set of halftone dots. For such conversion, a lithographic silver halide photographic light-sensitive material is used, and a document is photographed through a cross screen or a contact screen. Then, the concentration of sulfite ion is very low and the so-called hydroquinone developing agent is contained. A halftone image is formed by developing with a lith type developer. The squirrel-type silver halide photographic light-sensitive material has a gamma of at most 5 to 6 even when treated with an ordinary developer having a high sulfite ion concentration, for example, a commercially available developer for photographic paper. Since there are many fringes that must be avoided, it is said that the combination with the lith-type developer is indispensable for negative / positive halftone dots. For more information on this squirrel-type developer, see J.A.C.Ale's Journal of the Franklin Institute (JAC Yule: J.Frank).
lin Institute), 239, p. 221 (1945), which essentially contains only hydroquinone as a developing agent and serves as an antioxidant for the developing agent. It is a developer having a low concentration.

Since such a developing solution has poor homeostasis and is easily subjected to autoxidation, in order for a platemaker to always obtain a high-quality halftone negative or halftone positive image, the activity of the developer which is decreasing with time is decreased. It is necessary to control the developing solution in order to keep constant, but it is unavoidable that the operation becomes complicated.

Furthermore, in the lith development processing, there are two major disadvantages in that the processing speed is slow in addition to the control of the developing solution for keeping the activity constant.

As the flow of printing plate making in recent years, the shortening and shortening of the printing process can be mentioned, and the demand for the processing speed of the plate making film is increasing.

As a technique for obtaining an image of extremely high contrast suitable for plate making using a developer having a high preservative property, for example, Japanese Patent Application No. 59-240147 and the like use a silver halide photographic light-sensitive material containing a tetrazolium salt. A method is disclosed. With this method, it is possible to use a stable developer having a high sulfite ion concentration, and it is possible to perform a rapid processing of a developing time of around 30 seconds, which is not possible with conventional lith development, and a time required for completion of drying of 90 seconds to 100 seconds. is there.

On the other hand, a silver halide photographic light-sensitive material for plate making is generally required to have so-called ortho-type photosensitivity, which has photosensitivity in the green part.

Since the photosensitive silver halide emulsion alone has a narrow photosensitive wavelength range, a spectral sensitizer is used for the purpose of extending the photosensitive wavelength range to long-wave distance measurement. For example, Japanese Patent Publication No. 38-7828 is used to impart sensitivity to green light.
No. 40, No. 40-392, No. 43-10251, No. 43-22884, British Patent Nos. 815,172, No. 955,961, No. 955,912, No. 142,228.
U.S. Pat.Nos. 1,942,854, 1,950,876, 1,957,86
No. 9, No. 2,238,231, No. 2,521,705, No. 2,647,059,
JP-B-43-2606, 44-3644, 46-18106, 46-1
No. 8108, No. 48-15032, No. 49-33782, No. 54-34252,
58-52574, U.S. Patents 2,839,403, 3,567,458,
Examples thereof include cyanine dyes and merocyanine dyes described in the specification such as 3,625,698.

[Problems to be solved by the invention]

These spectral sensitizers not only enhance the sensitivity in a specific wavelength region, but at the same time, as a general characteristic, for example, (a) are not affected by other additives or do not affect the effects of the additives. (B) No change in photographic characteristics such as a decrease in sensitivity or an increase in fog even after the lapse of time (c) Properties such as no dye stain after processing are required. In the case of relatively rapid development, dye contamination after processing becomes large, which is a serious problem in practical use.

In order to reduce dye contamination, there is little dyeing property to hydrophilic colloid such as gelatin, and it is easy to flow into the processing liquid.
It suffices to use a spectral sensitizer having high solubility, and various compounds have been proposed in the past. However, the spectral sensitizer often has a great effect on the development effect that gives an extremely high contrast required for plate making, and it causes problems such as lowering the contrast. It was difficult to apply the solution as it is to a silver halide photographic light-sensitive material for high-contrast development.

The object of the present invention is to solve the above-mentioned problems, to obtain extremely high contrast by rapid development processing using a high-sensitivity, high-sulfite ion-conventional developing solution, and dye contamination after processing. The object is to provide a silver halide photographic light-sensitive material having an extremely small amount.

[Means for solving problems]

As a result of various studies, the present inventors have found that in a silver halide photographic light-sensitive material having a support and a hydrophilic colloid layer coated on the support, the hydrophilic colloid layer containing at least one silver halide emulsion layer. The silver halide grains contained in the colloid layer are spectrally sensitized by the compound represented by the following general formula [I], and the hydrophilic colloid layer has the following general formula [S].
It has been found that the above object can be achieved by a silver halide photographic light-sensitive material characterized by containing a compound represented by

General formula [I] 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, chlorine atom, bromine atom), an unsubstituted alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group,
Butyl group, hexyl group, etc.), alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, propoxy group,
Butoxy group), hydroxy group, alkoxycarbonyl group having 2 to 6 carbon atoms (eg methoxycarbonyl group, ethoxycarbonyl group), alkylcarbonyloxy group having 2 to 5 carbon atoms (eg acetyloxy group, propionyloxy group, etc.), phenyl Group, hydroxyphenyl group, and the like.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, and 4-phenyloxazole as oxazole nuclei; benzoxazole, 5-chlorobenzoxazole as benzoxazole nuclei; 5-bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole,
5-ethoxycarbonylbenzoxazole, 5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 6-methoxybenzoxazole, 5,6-dimethylbenzoxazole, 6-chloro-5-methylbenzoxazole, etc. Examples of the naphthoxazole nucleus include naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] oxazole, and the like.

R ¹ represents an unsubstituted or substituted alkyl group. Examples of the substituent include a hydroxy group, a sulfo group, a sulfonate group,
Carboxy group, halogen atom (for example, fluorine atom, chlorine atom), unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (alkoxy group may be further substituted with sulfo group or hydroxy group), 2 to 5 carbon atoms Alkoxycarbonyl group, alkylsulfonyl group having 1 to 4 carbon atoms, sulfamoyl group, unsubstituted or substituted carbamoyl group (having 1 carbon atom
A substituted carbamoyl group substituted with an alkyl group of 4 to 4), a substituted phenyl group (examples of the substituent are a sulfo group, a carboxy group, a hydroxy group, etc.), a vinyl group, and the like.

Specific examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the substituted alkyl group include 2-hydroxyethyl group and 3-hydroxypropyl group as hydroxyalkyl group, and 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group and 4-sulfobutyl group as sulfoalkyl group,
2-hydroxy-3-sulfopropyl group, 2-chloro-
Carboxyalkyl group such as 3-sulfopropyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, etc., 2,2,2-trifluonoethyl group, 2
-(3-Sulfopropyloxy) ethyl group, 2- (2-
Hydroxyethoxy) ethyl group, ethoxycarbonylethyl group, methylsulfonyl group, 2-sulfamoylethyl group as sulfamoylalkyl group, 2-carbamoylethyl group, 2-N, N-dimethylcarbamoylethyl group, and phenethyl group , P-carboxyphenethyl group, p-sulfophenethyl group as sulfoaralkyl group, o-
Examples thereof include a p-hydroxyphenethyl group, an allyl group, a phenoxyethyl group and the like such as a flufophenethyl group.

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,
Alternatively, it represents a substituent CH _{2 n} A or CH _{2 n} OCH _{2 n} A. Here, A is a nitrile group, an alkylsulfonyl group,
Represents a sulfamoyl group, an alkylsulfonylamino group, or an alkoxy group (preferably having a carbon number of 1 to 8),
n represents a value of an integer of 1 to 4.

Each of the above groups also includes 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 include an alkoxycarbonylalkyl group in which an alkyl group is substituted with a halogen atom (for example, a methoxycarbonylfluoromethyl group, an ethoxycarbonylfluoromethyl group, a fluoroethoxycarbonylethyl group, etc.) and a hydroxyalkyl group (for example, 2 -Hydroxyfluoroethyl group, 2-hydroxyfluoropropyl group, 3-hydroxyfluoropropyl group, 2,3-dihydroxyfluoropropyl group, etc., hydroxyalkoxyalkyl group (for example, hydroxymethoxyfluoromethyl group, 2- (2-hydroxyfluoropropyl group) (Ethoxy) ethyl group, 2-hydroxyfluoroethoxymethyl group, etc.), carbamoylalkyl group (N-
Alkyl-substituted, N, N-dialkyl-substituted, N-hydroxyalkyl-substituted, N-alkyl-N-hydroxyalkyl-substituted, N, N-di (hydroxyalkyl) -substituted substituted carbamoylalkyl groups and cyclic amines on pages 5 and 6 A carbamoylalkyl group of) (for example, 2-carbamoylchloroethyl group, 2-N- (2-hydroxyethyl) carbamoylchloroethyl group, N-hydroxyfluoroethylcarbamoylmethyl group, N, N-di (2-hydos) Xyfluoroethyl) carbamoylmethyl group, 2-N, N-di (2-hydroxyethyl) carbamoylchloroethyl group, N, N-dimethylcarbamoylchloromethyl group, serforinocarbamoylchloromethyl group, piperidinocarbamoylmethyl group Etc.), hydosoxyphenyl group, carbon number 7
~ 9 hydroxyalkylphenyl groups (eg p- (2
-Hydroxyfluoroethyl) phenyl group, m- (1-
(Hydroxyfluoroethyl) phenyl group) or the substituents CH _{2 n} A or CH _{2 n} OCH _{2 n} A. Here, A is a nitrile group, an alkylsulfonyl group,
It represents a sulfamoyl group, an alkylsulfonylamino group, or a lower alkoxy group. Among them, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (eg, methylsulfonyl group, ethylsulfonyl group, etc.), and sulfamoyl The group is preferably a sulfamoyl group having 1 to 4 carbon atoms (for example, N-methylsulfamoyl group, N, N-dimethylsulfamoyl group, etc.), and the alkylsulfonylamino group preferably has 1 to 4 carbon atoms. 4 alkylsulfonylamino groups (such as a methylsulfonylamino group), a lower alkoxy group is
Preferably, it is 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 and each is a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 4, such as a methyl group or an ethyl group), an alkoxy group (preferably having a carbon number of 1 to 4). (Eg, methoxy group, ethoxy group, etc.), sulfoalkyl group, sulfo group, chlorine atom, fluorine atom, or carboxy group.

In the compound represented by the above general formula [I], 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, sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-flufobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3-sulfo-2-
Examples thereof include a hydroxypropyl group.

Next, typical specific examples of the compound represented by the above general formula [I] used in the present invention will be given, but it goes without saying that the compound used in the present invention is not limited thereto.

[Exemplified compound] The compounds represented by the above general formula [I] used in the present invention are, for example, JP-B-46-549, JP-B-46-18105, and JP-B-46-18106.
Nos. 46-18108, 47-4085, 58-52574, U.S. Patents 2,839,403, 3,384,486, 3,625,698, and
It can be synthesized according to the method for synthesizing dimethine merocyanine described in 3,480,439 and 3,567,458.

The merocyanine dye represented by the above general formula [I] used in the present invention can be added and dispersed in a silver halide emulsion by various methods, for example, conventionally known methods. For example, a method of dispersing and adding together with a surfactant described in JP-B-49-44895 and JP-A-50-11419, JP-A-53-16624 and JP-A-53-102732.
No. 53-102733, U.S. Pat.Nos. 3,469,987, 3,676,
The method of adding as a dispersion with a hydrophilic substrate described in the specification of No. 147, the method of adding as a solid solution described in the specification of East German Patent 143,324 and the like can be mentioned. In addition, the merocyanine dye may be added to the emulsion by dissolving it in a water-soluble solvent such as water, ethanol, methanol, acetone, n-propanol, fluorinated alcohol, or pyridine 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 such that spectral sensitization of a silver halide emulsion is carried out, for example, x10 ^-5 to 2 x 10 ^-2 mol, preferably 1 x 10 ^-4 mol per mol of silver halide. ~ 2 x 10 ^-3 mol.

Formula [S] _{YS-L 1 - (J 1} ) k - (L 2) l - (Z) m - (L 3) n - (J 2 L 4)
_p (G) _q ] _{r In the} formula, L _{1 to} L ₄ are each a divalent hydrocarbon group, and J ₁ and J ₂ are each —O—, —COO—, —CONR ¹ —, —SO ₂ NR ¹ −, −NR ¹ −C
^{O-NR 2 -, - SO} 2 -, - N = N -, - NR 2 - or -CO-
, Y is a hydrogen atom, a divalent bond or an amidino group, and
Is a heterocyclic group, G is a sulfonic acid group, a carboxyl group or a phosphoric acid group, R ¹ and R ² are each a hydrogen atom, an alkyl group or an aryl group, and k, l, m and n are integers of 0 to 2 , P is 0
4 is an integer, q is an integer of 1 to 4, and r is an integer of 1 to 2.

However, when G is a carboxyl group, m represents an integer of 1 to 2, and when Y represents a divalent bond, r represents 2.

In the general formula [S], examples of the divalent hydrocarbon group represented by L _{1 to} L ₄ include an alkyl group, an arylene group and an aralkylene group, and the alkylene group is a chain having 1 to 15 carbon atoms. And cyclic groups are preferred, and examples thereof include methylene, ethylene, propylene, pentamethylene, dodecamethylene, and 1,6-cyclohexylene.

Examples of the arylene group represented by L ₁ and L ₂ include 1,4-
There are groups such as phenylene, 1,3-phenylene, 1,4-naphthylene, and 1,4-anthraquinolylene, and examples of the eralkylene group include groups such as benzylene and phenethylene.

The amidino group represented by Y includes those having a substituent, and examples of the substituent include an alkyl group (each group such as methyl, ethyl and benzyl), an aryl group (each group such as phenyl, p-tolyl and naphthyl). ), A heterocyclic group (2-thiazolyl,
Each group such as 2-pyridyl, 4-imidazolyl and the like) and the like can be mentioned.

The heterocyclic group represented by Z is preferably a 5-membered to 7-membered cyclic group, and includes those condensed with a benzene ring, a naphthalene ring, a 5-6 membered heterocyclic ring or a 5-6 membered aliphatic ring. , Specifically, furan, thiophene, benzo [b] thiophene, imidazole, benzimidazole, pyrrole, s-
Each heterocycle such as triazine, pyrimidine, quinoline, indole, benzoxazole, benzothiazole and the like can be mentioned.

Examples of the alkyl group represented by R ¹ and R ² include groups such as methyl, ethyl and propyl, and examples of the aryl group include groups such as phenyl and naphthyl.

Furthermore, a divalent hydrocarbon group represented by L _{1 to} L ₄ , R ¹ and R ²
The alkyl group, aryl group represented by and the heterocyclic group represented by Z include those having a substituent, and examples of the substituent include an alkyl group (each group such as methyl, ethyl, sec-propyl) and an alkoxy group ( Methoxy, ethoxy, se
c-propyl, t-octyl, etc.), amino group (methylamino, N, N-dimethylamino, butylamino, etc. groups), aryl group (tolyl, phenyl, etc. groups), aryloxy group ( Each group such as phenoxy and naphthoxy) mercapto group, sulfonic acid group, carboxyl group, cyano group,
Carbamoyl group, sulfamoyl, amide group (each group such as acetylamino and benzoylamino), sulfonyl group (group such as methanesulfonyl and benzenesulfonyl), alkoxycarbonyl group (ethoxycarbonyl group), aryloxycarbonyl group (phenyloxycarbonyl) , An acyl group (each group such as acetyl, benzoyl, propionyl) and a heterocyclic group (each group such as thienyl, oxazolyl, cinnolyl), for example, -J ₂ L ₄ G, -J ₁ -L ₁ -SII
(J ₁ , J ₂ , L ₁ , L ₄ , and G are as defined above).

The carboxyl group, sulfonic acid group and phosphoric acid group represented by G may be acid-free or may form a counter salt,
As the counter salt, there are inorganic cations such as alkali metals (Na, K, Li), alkaline earth metals (Ca, Mg) and ammonium, or organic ammonium such as pyridinium, triethylammonium, triethanolammonium and guanidinium. Further, an inner salt may be formed.

The compound of the general formula [S] used in the present invention is Y
The mercapto-substituted anion derivative [S-
I], pseudo-thiuronium inner salt derivative [SI
I] and disulfide derivative [S-III],
Typical specific examples of these are shown below. The present invention is not limited to these.

Exemplified compound SI-25 HS ・ (CH₂)₂SO₃HS-I-27 HS (CH₂)_FourSO₃K S-I-28 NaS (CH₂)_FiveSO₃NaSI-30 HSCH₂CH₂CO (CH₂)₃OPO (OH)₂  The compound represented by the general formula [S] is, for example, J. Am. Chem. So.
c.,77, 6231 (1955), J. Heterocycl. Chem., 1968,Five
(3) 319-22, Arm.Khim.Zh., 1967,20(10), 832-5 etc.
It can be easily synthesized by referring to the literature.

That is, generally, a pseudo-thiuronium inner salt derivative [S-II] can be obtained by addition reaction in an aqueous solvent (eg, methanol, ethanol, hydrous ethanol) according to the following scheme.

The sulfide derivative [S- which is a part of the compound of the present invention
[I] is synthesized by hydrolyzing [S-II] shown in the above scheme in a mild alkaline atmosphere. Specifically, it can be isolated as a guanidinium salt by heating in an aqueous ammonia solution. The guanidinium salt can be converted into any salt by ion exchange treatment or salt exchange operation.

The sulfide derivative [SI] is another compound of the present invention which is a disulfide derivative [S-III] by oxidation.
Be led to.

L _{1 to} L ₄ , J _{1 to} J ₂ , Z, G, k, l, m, n, p in the formulas [I], [SI], [S-II] and [S-III], q and r have the same meanings as in the general formula [S], s ¹ and s ² are each 1, and s ₃ is 2.

In the formula [I], Nu represents a nucleophilic group, and examples thereof include a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, and trifluoromethylsulfonyloxy.

R ³ and R ⁴ in the formula [II] each represent a mercury atom, an alkyl group, an aryl group or a heterocyclic group.

The amount of the compound of the general formula [S] contained in the silver halide photographic light-sensitive material of the present invention is 5 × 10 ⁻⁶ per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention.
The range of 5 × 10 ^-1 mol is preferable, and further 5 × 10 ^-5 to 1 ×
It is preferably in the range of 10 ^-2 mol.

The silver halide photographic light-sensitive material of the present invention comprises a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support. The silver halide emulsion is directly coated on the support. It may be coated or may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer may be further coated as a protective layer on the silver halide emulsion layer. The silver halide emulsion layers 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 be provided with 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 compound of the general formula [S] of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and / or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

To incorporate the compound of the general formula [S] of the present invention into the hydrophilic colloid layer, a method of dissolving the compound of the general formula [S] in appropriate water and / or an organic solvent or adding it to an organic solvent is used. Examples thereof include a method in which the solution is dispersed in a hydrophilic colloid matrix of gelatin or a gelatin derivative and then added, or a method in which the solution is dispersed and added in latex.

The silver halide used in the silver halide photographic light-sensitive material of the present invention is preferably silver chlorobromide or silver chloroiodobromide containing at least 50 mol% of silver chloride. The average grain size of the silver halide grains is preferably 0.05 to 0.5 μm, more preferably 0.10 to 0.40 μm.

Regarding the monodispersity of the silver halide emulsion used in the present invention, the value is preferably 5 to 25, more preferably 8 to 20.
To be prepared. The grain size of the silver halide grains used in the present invention is conveniently represented by the ridge length of cubic grains, and the monodispersity S is a value obtained by dividing the standard deviation of grain sizes by the average grain size as shown in the following formula (1). Is expressed as a value multiplied by 100.

Further, as the silver halide usable in the present invention, for example, a type having a multilayer laminated structure of at least two layers can be used. For example, silver chlorobromide grains in which silver chloride is used in the core portion, silver bromide in the shell portion, conversely silver bromide in the core portion and silver chloride in the shell portion may be used. At this time, iodine can be contained in any layer within 5 mol%.

When the silver halide emulsion used in the present invention is prepared, a rhodium salt may be added to control sensitivity or gradation. The addition of the rhodium salt is generally preferred during grain formation, but may be during chemical ripening or preparation of the emulsion coating solution.

In this case, the rhodium salt may be a simple salt or a double salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride and the like are used.

The addition amount of the rhodium salt can be freely changed depending on the required sensitivity and gradation, but a range of 10 ^-8 mol to 10 ^-6 mol per 1 mol of silver is particularly useful.

When the rhodium salt is used, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt and gold salt may be used together. Iridium salts are often used for the purpose of imparting high illuminance characteristics, and 10 ^-8 to 10 ^-6 mol per 1 mol of silver is used.
It can be preferably used up to a molar range.

The silver halide used in the present invention has the general formula [I]
In addition to the spectral sensitization with the compound (1), it can be sensitized with various chemical sensitizers. Examples of the sensitizer include active gelatin, sulfuric acid sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, etc.) Selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.) Reduction Sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chloroaurite, potassium aurothiocyanate, potassium chloroaurate,
2-aurosulfobenzothiazole methyl chloride,
Various noble metal sensitizers represented by ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite and the like can be used alone or in combination of two or more. When a gold sensitizer is used, rhodan ammon can be used as an auxiliary agent.

The spectrally sensitized silver halide used in the present invention and the compound represented by the general formula [S] are allowed to be present in the hydrophilic colloid layer. The hydrophilic colloid used particularly advantageously in the present invention is as follows. Gelatin is preferred, and examples of hydrophilic colloids other than gelatin include colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivative. , For example US Pat.
614,928, 2,525,753, phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin, or U.S. Pat.No. 2,548,520.
No. 2,2,831,767, such as those obtained by graft-polymerizing a polymerizable monomer having an ethylene group such as styrene acrylate, acrylic acid ester, methacrylic acid, methacrylic acid ester, etc. onto gelatin. Examples of the hydrophilic colloids include silver halide-free layers such as antihalation layers, protective layers,
It can also be applied to the intermediate layer and the like.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Representative examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films and the like. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

The light-sensitive material according to the present invention contains the compound represented by the general formula [S] of the present invention in a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support as described above. However, it has a suitable film thickness on the silver halide emulsion layer, preferably 0.1 to 10 .mu.m, and particularly preferably 0.8.
It is particularly preferable to have a constitution in which a hydrophilic colloid layer having a thickness of ˜2 μm is applied as a protective layer.

In the silver halide emulsion layer and the hydrophilic colloid layer used in the present invention, various photographic additives such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers and anti-photosensitive agents may be added if necessary. Stain agent, pH adjuster, antioxidant,
An antistatic agent, a thickener, a graininess improver, a dye, a moldant, a whitening agent, a developing speed adjusting agent, a matting agent and the like can be used within the range that the effects of the present invention are not impaired.

Of the above various additives, those which can be particularly preferably used in the present invention include, as a thickener or a plasticizer, for example, U.S. Pat.No. 2,960,404, Japanese Patent Publication No. 43-4939, West German Application Publication No. 1,904,604. Book, JP-A-48-63715,
Japanese Patent Publication No. 45-15462, Belgian Patent No. 762,833,
U.S. Pat.No. 3,767,410, substances described in each specification of Belgium Patent No. 558,143, for example, styrene-sodium maleate copolymer, dextran sulfate, etc.
As a hardener, various hardeners such as aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinylsulfone-based, isocyanate-based, sulfonate-based, carbodiimide-based, mucochloric acid-based, and acyloyl-based hardeners, UV absorption As the agent, for example, U.S. Patent No. 3,253,921,
The compounds described in the respective specifications of British Patent No. 1,309,349, especially 2- (2'-hydroxy-5-tertiarybutylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-3) Butylphenyl) benzotriazole, 2- (2-hydroxy-3-tertiarybutyl-5-butylphenyl) -5-chlorobenzotriazole, 2-
(2-Hydroxy-3,5-di-tertiarybutylphenyl)-
5-chlorobenzotriazole etc. can be mentioned,
As the dye, U.S. Patent No. 2,072,908, German Patent No. 107,990, U.S. Patent No. 3,048,487, U.S. Patent No. 515,
The compounds described in each specification such as No. 988 can be used, and these compounds may be contained in a protective layer, an emulsion layer, an intermediate layer or the like. Further, as coating aids, emulsifiers, penetrating agents for treating liquids, antifoaming agents or surfactants used for controlling various physical properties of photosensitive materials, British Patent No. 548,532, and 1,221,9
No. 80, U.S. Pat. Examples thereof include silica gel, a polymer of polymethylmethacrylate having a particle size of 0.5 to 20 μm, and the like.

The silver halide photographic light-sensitive material containing the compound of the general formula [S] of the present invention in the silver halide emulsion layer and / or another hydrophilic colloid layer is present in the presence of the compound represented by the following general formula [III]. It is preferable to develop with.

General formula (III) [In the formula, R ³¹ represents a 5- or 6-position nitro group, and R ³² represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. M
Represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium ion. Specific examples of the compound represented by the general formula [III] include 5-nitroindazole and 6-nitroindazole, but the present invention is not limited thereto.

The compound represented by the general formula [III] is an organic solvent such as diethylene glycol, triethylene glycol, ethanol, diethanolamine and triethanolamine,
It may be dissolved in an alkali such as sodium hydroxide and an acid such as acetic acid and added to the developer, or may be added as it is.

The compound represented by the general formula [III] is preferably about 1 mg to 1,000 mg, and more preferably about 50 mg per developer.
Contained in the concentration range of mg to 300 mg.

The developing agents for the silver halide photographic light-sensitive material of the present invention, especially the black-and-white photographic light-sensitive material, include the following. This developing agent can be used together with the compound represented by the above general formula [III].

HOCH = CH _n OH type developing agents include hydroquinone, and catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, tolhydroquinone, methylhydroquinone, and 2,3. -Dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dipromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-
Dibenzoylaminohydroquinone, catechol, 4-
Examples include chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4- (2-hydroxybenzoyl) pyrogallol, sodium ascorbate and the like.

Further, as the HOCH = CH _n NH ₂ type developer, ortho and para aminophenols or aminopyrazolones are typical ones, and 4-aminophenol and 2-amino-6-
Phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, 2,4-cyaminoresorcinol , 2,4,6
-Triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Further, as the H ₂ NC = C _n NH ₂ type developer, for example, 4
-Amino-2-methyl-N, N-diethylaniline, 2,4-
Diamino-N, N-diethylaniline, N- (4-amino-3-methylphenyl) -morpholine, p-phenylenediamine, 4-amino-N, N-dimethyl-3-hydroxyaniline, N, N, N, N-tetramethylparaphenylenediamine, 4-amino-N-ethyl-N- (β-hydroxyethyl) -aniline, 4-amino-3-methyl-N-
Ethyl-N- (β-hydroxyethyl) -aniline, 4
-Amino-N-ethyl- (β-methoxyethyl) -3-
Methyl-aniline, 4-amino-3-methyl-N-ethyl-N- (β-methylsulfonamidoethyl) -aniline, 4-amino-N-butyl-Nn-sulfobutylaniline, 1- (4- Aminophenyl) -pyrrolidine, 6
-Amino-1-ethyl, 1,2,3,4-tetrahydroquinone and the like.

Heterocyclic developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl. -4-methyl-4
3-pyrazolidones such as -hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, 1- (p-aminophenyl) -3-amino-2-
Pyrazoline, 1-phenyl-3-methyl-4-amino-
Examples thereof include 5-pyrazolone and 5-aminouracil.

Others, The Theory of the Photographic Process 4th Edition
Photographic Process, Fourth Edition) pages 291-334 and the Journal of the American Chemical Societ.
y) Developers described in Vol. 73, page 3,100 (1951) and the like can be effectively used for the silver halide photographic light-sensitive material of the present invention.

These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination. Even if a sulfite such as potassium sulfite or ammonium sulfite is used as a preservative in the developer used for processing the light-sensitive material of the present invention, the effect of the present invention is not impaired. There are two characteristics.
Moreover, you may use hydroxylamine and a hydrazide compound as a preservative. In addition, it is necessary to adjust the pH and provide a buffer function with caustic alkali, alkali carbonate, amine, etc. as used in general black and white developers, and to suppress inorganic development such as promkari and organic development inhibitors such as benzotriazole, ethylenediaminetetraacetic acid, etc. Metal ion scavengers, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxides, sodium alkylaryl sulfonates, natural saponins, surfactants such as sugars or acryl esters of the above compounds, glutaraldehyde, formalin. It is optional to add a hardening agent such as glyoxal and an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamine include triethanolamine diethanolamine, ethanolamine trimethylamine 2-diethylamino-1-ethanol 2-methylamino-1-ethanol 3-diethylamino-1-propanediol 3-diethylamino-1-propanol 5-amino- 1-Pentanol diethylamine methylamine triethylamine dipropylamine di-isopropylamine 3,3'-diaminodipropylamine 3-dimethylamino-1-propanol hydantoin acid allylamine ethylamine dimethylamine ethylenediamine 2-dimethylaminoethanol 2-ethylaminoethanol 2 -(2-aminoethylamino) ethanol tetramethylammonium acetate choline choline chloride Droxylamine sulfate 2-[(2-aminoethylamine) -ethylamino] -ethanol aminoguanidine sulfate 6-aminohexanoic acid 3-amino-1-propanol 1-dimethylamino-2-propanol 2-hydroxy-4-thiadecyl Trimethylammonium (pta) Pyridine Glycine o-Aminobenzoic acid Polyethyleneimine L-(+)-Cysteine hydrochloride Benzylamine 2-Amino-1-ethanol 4-Amino-1-butanol 3- (Dimethylamino) -1,2 -Propanediol 3-Moliphorino-1,2-propanediol 1,4-piperazine bis (ethanesulfonic acid) 3-piperidino-1,2-propanediol N-piperidine ethanol and the like.

Examples of the above glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol and the like, and diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g, preferably 20 to 200 g, per developer. These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention can be subjected to development processing using a developing solution containing a development inhibitor as described above to obtain a light-sensitive property excellent in storage stability.

The pH value of the developer having the above composition is 9 to 12, but the pH value is preferably in the range of 10 to 11 from the viewpoint of stability and photographic characteristics.

The silver halide photographic light-sensitive material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 50.
The temperature is preferably not higher than 0 ° C., particularly preferably around 30 ° C., and the developing time is generally completed within 3 minutes, but particularly preferably within 40 seconds often gives good results. Further, it is optional to employ processing steps other than the development, such as washing, stopping, stabilizing, fastening, and if necessary, steps of pre-curing and neutralization, which can be omitted as appropriate. Furthermore, these processes may be so-called hand development processes such as plate development and frame development, or mechanical development such as roller development and hanger development.

〔Example〕

A silver chlorobromide emulsion was prepared using solutions A, B and C shown below.

<Solution A> Ocein gelatin 17g Polyisopropylene-polyethyleneoxydisuccinate sodium salt 5ml 10% ethanol solution distilled water 1280cc <Solution B> Silver nitrate 170g Distilled water 410ml <Solution C> Sodium chloride 40.9g Potassium bromide 35.7g Potaisopropylene oxydisuccinate sodium salt 10% ethanol solution 3 ml ossein gelatin 11 g distilled water 407 ml Solution A was kept at 40 ° C. and then sodium chloride was added so that the EAg value became 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 gradually increased over a total addition time of 80 minutes while the EAg was kept constant.

The EAg value was changed from 160 mv to the EAg value of 120 mv using a 3 ml / l sodium chloride aqueous solution 5 minutes after the start of the addition, and thereafter this value was maintained until the completion of mixing.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol / l sodium chloride aqueous solution.

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

In addition, a variable flow rate roller tube metering pump was used to add solutions B and C.

Further, during the addition, it was confirmed by observing with an electron microscope that no new grains were found in the system due to sampling of the emulsion.

Also, during the addition, the pH value of the system was controlled with a 3% nitric acid aqueous solution so as to keep it constant at 3.0.

After the addition of solutions B and C, the emulsion was ripened in Ostwald for 10 minutes, then desalted and washed with water in the usual manner, and then 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) was added at 55 ° C. Disperse by stirring for 30 minutes, then 750c
Prepared in c.

The emulsion was then gold sulfur sensitized and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. The emulsion was divided and the compound of the general formula [I] according to the present invention as shown in Table 2 or a sensitizing dye ([I]-(a) to (f)) shown below for comparison 3 × 10 ⁻ Dye sensitization was carried out by adding ⁴ mol / mol Ag, and 700 mg / Ag 1 mol of the general formula [S] was added to each emulsion as shown in Table 2.
-Sodium dodecylbenzene sulfonate 600 mg / Ag 1 mol, 2,3,5-tri (p-methylphenyl) tetrazolium chloride 600 mg / Ag 1 mol, styrene-maleic acid copolymer 2 g / Ag 1 mol were added, and on a polyethylene terephthalate film. Ag3.5g / m ^2, was coated so as to become the amount of gelatin 20 g / m ^2. In that case, 30 mg / m ² of 1-decyl-2- (3-isopentyl) succinate 2-sulfonate as a spreading agent and 25 mg / m ² of formalin as a hardening agent are used so that the amount of gelatin becomes 1.0 g / m ^2. A hard film protective layer was applied in multiple layers.

Comparative sensitizing dye Three pieces of each of the obtained samples were taken, one piece was subjected to an optical wedge using a sensitometer and stepwise exposure was performed with tungsten light, and the other piece was contact screen GN No. manufactured by Dainippon Screen Mfg. Co., Ltd. 2 (150 L) was used to perform halftone exposure with xenon light. The remaining one piece was subjected to the next treatment without exposing it.

The above sample piece was processed in an automatic developing machine having a developing tank capacity of 40 l using a developing solution having the following formulation and a commercially available fixing solution.

[Development processing conditions]

(Process) (Temperature) (Time) Development 28 ℃ 30 seconds Fixing 28 ℃ 20 seconds Washing 20 ℃ 20 seconds Drying 40 ℃ 20 seconds [Developer composition] When the developer was used, the above composition A and composition B were dissolved in this order in 500 ml of pure water and finished to 1 before use.

For the developed sample that was subjected to wedge exposure, write a photographic characteristic curve and set the sensitivity at optical density 2.5 to sample No. 1
The relative value is calculated based on
The tan θ values of the straight line parts up to are shown.

The quality of the formed mesh (dot quality) was evaluated for those photographed with a printing plate camera using xenon light.

As for the dot quality, for so-called 50% dots where the area of the halftone dot area and the area of the clear area are equal, the state of the fringe (blurring) that occurs around the halftone dot is visually judged and the fringe with a small fringe is 5
It was evaluated by the five-level display. That is, "5" is excellent and "1" is extremely bad. If the 50% dot quality is below "3", this is generally unacceptable.

In addition, for the sample processed without exposure, 4 sheets were piled up, and the residual color of the film was visually evaluated and evaluated in 5 levels. "5" was colorless and "1" was a strong orange residual color. Indicated. For general platemaking, the residual color of less than "3" is a major drawback.

The results are shown in Table 3.

As shown in Table 3, it contains a compound of the general formula [S] which is color-sensitized by the sensitizing dye of the general formula [I] according to the present invention. The sample (No.1-11) has a relative sensitivity of 94 to 125, which is higher than that of the comparative sample (No.12 to 18.85 or less), and the gamma is 16 to 20, which is extremely hard and has a dot quality rank and a residual quality. Since the color ranks are superior to the comparative sample, it can be seen that the sample has less residual color.

Also, the effect of the present invention was confirmed for the samples using compounds SI-2, SI-17, S-III-1, S-III-2 instead of compound SI-21 in sample No. 11. .

〔The invention's effect〕

As described above, the silver halide photographic light-sensitive material of the present invention comprises
It has an effect that an extremely high contrast can be obtained by rapid development processing using a general developing solution having a high photosensitivity and a high sulfite ion concentration, and that the dye contamination after the processing is extremely small.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a support and a hydrophilic colloid layer coated on the support, the hydrophilic colloid layer including at least one silver halide emulsion layer. A silver halide photograph characterized in that silver halide grains are spectrally sensitized with a compound represented by the following general formula [I], and the hydrophilic colloid layer contains a compound represented by the following general formula [S]. Photosensitive material. General formula [I] [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 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 n} OCH _{2 n}
Represents A. Here, A is a nitrile group, an alkylsulfonyl group, a sulfamoyl group, an alkylsulfonylamino group,
Alternatively, it represents an 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 sulfoalkyl group, a sulfo group, a chlorine atom, a fluorine atom or a carboxy group. ] Formula [S] _{YS-L 1 - (J 1} ) k - (L 2) l - (Z) m - (L 3) n - (J 2 L 4)
_p (G) _q ] _{r In the} formula, L _{1 to} L ₄ are each a divalent hydrocarbon group, and J ₁ and J ₂ are each —O—, —COO—, —CONR ¹ —, —SO ₂ NR ¹ −, −NR ¹ −C
^{O-NR 2 -, - SO} 2 -, - N = N -, - NR 1 - or -CO-
, Y is a hydrogen atom, a divalent bond or an amidino group, and
Is a heterocyclic group, G is a sulfonic acid group, a carboxyl group or a phosphoric acid group, R ¹ and R ² are each a hydrogen atom, an alkyl group or an aryl group, and k, l, m and n are integers of 0 to 2 , P is 0
4 is an integer, q is an integer of 1 to 4, and r is an integer of 1 to 2. However, when G is a carboxyl group, m represents an integer of 1 to 2, and when Y represents a divalent bond, r represents 2.