JPS62265646A - Spectrally sensitized silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material ensuring high photosensitivity and contrast and causing little dye stain by spectrally sensitizing the silver halide in hydrophilic colloidal layers including a silver halide emulsion layer formed on a substrate with a specified compound and by incorporating a specified compound into the hydrophilic colloidal layers. CONSTITUTION:The silver halide particles in hydrophilic colloidal layers including at least one silver halide emulsion layer formed on a substrate are spectrally sensitized with a compound represented by formula I, and a compound represented by formula II is incorporated into the hydrophilic colloidal layers. In the formula I, Z is a group of nonmetallic atoms required to form an oxabenzole, benzoxazole or naphthoxazole ring, R<1> is alkyl, R<2> is alkoxycarbonylalkyl or other prescribed group and each of R<3> and R<4> is H, Cl, F or a prescribed group such as alkyl. In the formula II, Z1 is a group of atoms required to form a thiazole, selenazole or tellurazolium ring, each of R<21> and R<22> is H or a prescribed group such as alkyl, X<-> is an anion and m=0 or 1.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material spectrally sensitized with a novel merocyanine dye, and in particular has high green light sensitivity and high contrast halftone images. The present invention relates to a silver halide photographic light-sensitive material which can be obtained even in relatively rapid development and has extremely little dye staining after processing.

[Conventional technology]

It is well known that photographic images with extremely high contrast can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is about 0.5
Halogen containing fine grains of micrometers or less, narrow particle size distribution, and uniform grain shape, made of silver chlorobromide or silver chloroiodide emulsion with a high content of silver chloride, for example, 50 mol% or more. A method is known in which a high-contrast halftone image or line image is obtained by processing a silver oxide photosensitive material with an alkaline developer having a low concentration of sulfite ions and containing only hydroquinone as a developing agent.

This type of silver halide light-sensitive material is known as a lithium-type silver halide photographic light-sensitive material, and has an area of a size proportional to the continuous tone density change of the original during the photolithography process. It is used to convert to a set of halftone dots. Such conversion involves using a lithium-type silver halide photographic light-sensitive material, photographing the original through a cross-brocade screen or a contact screen, and then using a so-called lithium-ion silver halide photographic material, which has a very low sulfite ion concentration and contains only a hydroquinone developing agent. A halftone image is formed by developing with a Lith type developer. Even when this lithium-type silver halide photographic light-sensitive material is processed with a normal developer having a high sulfite ion concentration, such as a commercially available developer for photographic paper, the gamma is at most 5 to 6, and it is difficult to form halftone dots. Since there are many fringes that must be avoided, it is said that combination with the above-mentioned lithium-type developer is indispensable for halftone dot negatives/positives. - Yale Journal of the Franklin Institute (J, 8, CY
ule: J, Franklin In5
), Volume 239, Page 221 (1
945), which is essentially
This is a developer solution that contains only hydroquinone as a developing agent and has a low concentration of sulfite ions, which acts as an antioxidant for the developing agent.

Such developers have poor shelf life and are susceptible to auto-oxidation, so in order for plate makers to consistently obtain high-quality halftone negative or halftone positive images, they must reduce the activity of the developer, which decreases over time. Although it is necessary to manage the developer to maintain a constant value, it is unavoidable that the operation becomes complicated.

Furthermore, in the lithographic development process, there are two major disadvantages: in addition to the above-mentioned developer management that keeps the activity constant, the processing speed is slow.

The trend in printing plate making in recent years has been to shorten the printing process and shorten the time, and there is an increasing demand for processing speed of plate making film.

For example, Japanese Patent Application No. 59-240147 uses a silver halide photographic light-sensitive material containing a tetrazolium salt as a technique for obtaining an extremely high contrast image suitable for plate making using a developer with high stability. A method is disclosed. This method allows the use of a stable developer with a high concentration of sulfite ions, and enables rapid processing with a development time of around 30 seconds and a drying time of 90 to 100 seconds, which was not possible with conventional lithography. be.

On the other hand, silver halide photographic materials for plate making are -a
It is required to have so-called ortho-type photosensitivity, which is photosensitivity to green areas.

Since a photosensitive silver halide emulsion alone has a narrow wavelength range of sensitivity, a spectral sensitizer is used for the purpose of expanding the wavelength range of sensitivity to longer wavelengths. For example, as a device that imparts sensitivity to green light,
No. 28, No. 40-392, No. 43-10251, No. 43-22884, British Patent No. 815.172, No. 9
No. 55.961, No. 955,912, No. 142,22
No. 8, U.S. Patent No. 1942.854, U.S. Patent No. 1,950,8
No. 76, No. 1,957,869, No. 2.238.23
No. 1, No. 2,521,705, No. 2.647.059
No., Special Publication No. 43-2606, No. 44-3644, No. 46-18106, No. 46-18108, No. 48-
No. 15032, No. 49-33782, No. 54-342
No. 52, No. 58-52574, U.S. Patent No. 2,839.
No. 403, No. 3,567.458, No. 3,625,6
Examples include cyanine dyes and merocyanine dyes described in specifications such as No. 98.

[Problem that the invention seeks to solve]

These spectral sensitizers increase the sensitivity in a specific wavelength range, and at the same time have general properties such as (al) not being affected by other additives or affecting the effectiveness of the additives; (bl) Properties such as not causing changes in photographic characteristics such as decreased sensitivity or increased fog even after time has passed, and not causing dye staining after C1 processing are required, but the above comparison When rapid development is performed, dye staining after processing increases, which is a major problem in practice.

In order to reduce dye staining, it is necessary to use a material that has little staining property against hydrophilic colloids such as gelatin, and which easily flows out into the processing solution.
A spectral sensitizer with high solubility may be used, and various compounds have been proposed in the past.

However, in many cases, spectral sensitizers have a large effect on the development effect that provides the extremely high contrast required for plate making, resulting in problems such as a decrease in contrast. It was difficult to directly apply the solution to silver halide photographic materials that undergo high-contrast development.

The purpose of the present invention is to solve the above-mentioned problems, to obtain extremely high contrast through rapid processing using a normal developing solution with high photosensitivity and high sulfite ion concentration, and to prevent dye contamination after processing. An object of the present invention is to provide a silver halide photographic light-sensitive material with extremely low levels of silver halide.

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

General formula (1) Z represents an atomic group necessary to complete an oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus, and these nuclei may have a substituent on a carbon atom. Specific examples of substituents include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), unsubstituted alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group). etc.), alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, propoxy group,
butoxy group), hydroxyl group, alkoxycarbonyl group having 2 to 6 carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), alkylcarbonyloxy group having 2 to 5 carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), Examples include phenyl group, hydroxyphenyl group, and the like.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, 4-phenyloxazole, etc. as the oxazole nucleus; benzoxazole, 5-chlorobenzoxazole, and the like as the benzoxazole nucleus. 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6- Nut (1,2-
d) Nuclei such as oxazole, naphtho(2,1-d)oxazole, and naphtho(2,3-d)oxazole can be mentioned.

R1 represents an unsubstituted or substituted alkyl group.

Examples of substituents include hydroxy group, sulfo group, sulfonate group, carboxy group, halogen atom (e.g. fluorine atom, chlorine atom), unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (alkoxy group may further include sulfo group, may be substituted with a hydroxy group), an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a sulfamoyl group, an unsubstituted or substituted carbamoyl group (an alkyl group having 1 to 4 carbon atoms) (including substituted carbamoyl groups), substituted phenyl groups (examples of substituents include sulfo groups, carboxy groups, hydroxy groups, etc.), vinyl groups, 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 substituted alkyl groups include 2-hydroxyethyl and 3-hydroxypropyl groups as hydroxyalkyl groups, and 2-sulfoethyl and 3-hydroxypropyl groups as sulfoalkyl groups.
-Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2
-chloro-3-sulfopropyl group, carboxyalkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, 2,2.2-trifluoroethyl group, 2-(3-sulfopropyloxy)ethyl group, 2-(2-hydroxyethoxy)ethyl group, ethoxycarbonylethyl group, methylcarbamoylethyl group, 2-sulfamoylethyl group, 2-carbamoylethyl group, 2-N,N-dimethylcarbamoylethyl group as sulfamoylalkyl group groups such as phenethyl group, p-
p as carboxyphenethyl group, sulfoaralkyl group
-sulfophenethyl group, O-sulfophenethyl group, etc.
Examples include p-hydroxyphenethyl group, allyl group, and phenoxyethyl group.

R2 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 + CHz78 If (÷2 catty÷ (÷2
) represents ki. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or an alkoxy group having 1 to 8 carbon atoms, and n is 1 to 8.
Represents an integer value of 4.

Each of the above groups includes those having a substituent. For example, those in which the alkyl moiety of the above group is substituted with a halogen atom can also be preferably used. Examples of R2 include alkoxycarbonylalkyl groups in which each alkyl group is substituted with a halogen atom (e.g., methoxycarbonylfluoromethyl group, ethoxycarbonylfluoromethyl group, fluoroethoxycarbonylethyl group, etc.), hydroxya)
Ltkyl M (e.g. 2-hydroxyfluoroethyl group, 2-hydroxyfluoropropyl group, 3-hydroxyfluoropropyl group, 2,3-dihydroxyfluoropropyl group, etc.), hydroxyalkoxyalkyl group (e.g. hydroxymethoxyfluoromethyl group, 2-hydroxyfluoropropyl group, etc.) -(2-hydroxyfluoroethoxy)ethyl group, 2-hydroxyfluoroethoxymethyl group, etc.), carbamoyl alkyl group (N-alkyl substitution, N-N-dialkyl substitution, N-
hydroxyalkyl-substituted, N-alkyl-N-hydroxyalkyl-substituted, N,N-di(hydroxyalkyl)-substituted carbamoyl alkyl groups, and carbamoyl alkyl groups of 5- and 6-membered cyclic amines) (for example, 2-
Carbamoylcroconityl 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, cerfolinolupamoylchloromethyl group,
piperidinocarbamoylmethyl group, etc.), hydroxyphenyl group, hydroxyalkylphenyl group having 7 to 9 carbon atoms (e.g. p-(2-hydroxyfluoroethyl)phenyl 5, m = (1-hydroxyfluoroethyl)phenyl group, ,, TJg, bottom margin (\, ゛, etc.), or substituent +CHz-hA or +C
Represents H2-+TO 1,000 GHz+irA. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfamide group, an alkylsulfonylamine group, or a lower alkoxy group, and among these, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (for example, methyl sulfonyl group, ethylsulfonyl group, etc.), and the sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms (for example, N-methylsulfonamide group, N,
N-dimethylsulfonylamino group, etc.), the alkylsulfonylamino group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms (for example, methylsulfonylamino group, etc.), and the lower alkoxy group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms. 1 to 4 alkoxy groups (eg, methoxy group, ethoxy group, etc.).

n represents an integer value of 1-4.

R'l' and R4 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably one having 1 to 4 carbon atoms, such as a methyl group or an ethyl group), or an alkoxy group (preferably one having 1 to 4 carbon atoms, such as a methyl group or an ethyl group). 4, such as methoxy group, ethoxy group), alkyl sulfonic acid group, sulfonic acid group,
Represents a chlorine atom, a hydrogen atom, or a carboxy group.

Particularly preferred compounds of the above general formula (1) are those in which R1 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. Yes, specifically sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3-sulfo-2
-Hydroxypropyl group, etc.

Next, typical 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 compounds used in the present invention are not limited to these.

(I) 117r, m-1'1) (I)-1 (I) -6 (1) 7 0CH33(
h to CI)-10 CI)-13 CH2S(hK (1) -160CH* Hs CI)-18 (I)-20 CI)-22 C1,)-26 (I)-27 (C)It) nSOJ CI )-31 CI)-36 The compound represented by the above general formula (1) used in the present invention for CH2S03 is disclosed in Japanese Patent Publication Nos. 46-549 and 46-18105.
No. 46-18106, No. 46-18108, No. 47-4085, No. 58-52574, U.S. Patent 2
．． No. 839.403, No. 3,384,486, No. 3,
No. 625,698, No. 3,480.439, No. 3,5
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 67゜458 and the like.

The merocyanine dye represented by the general formula (1) used in the present invention can be added and dispersed in a silver halide emulsion by various methods, such as conventionally known methods. For example, the method of adding by dispersing with a surfactant described in the specifications of JP-B No. 49-44895 and JP-A-50-11419;
No. 24, No. 53-102732, No. 53-10273
No. 3, U.S. Patent No. 3,469,987, U.S. Patent No. 3,676
．． Examples include the method of adding as a dispersion with a hydrophilic substrate as described in the specification of No. 147, and the method of adding as a solid solution as described in the specification of East German Patent No. 143,324. In addition, the merocyanine dye may be dissolved in a water-soluble solvent such as water, ethanol, methanol, acetone, n-propanol, fluorinated alcohol, pyridine, etc. alone or in a mixture thereof and added to the emulsion. It may be added at any time during the emulsion manufacturing process, but preferably during or after chemical ripening. The amount of the merocyanine dye used in the present invention is the amount for spectral sensitization of the silver halide emulsion, for example, 10-S to 2 per mole of silver halide.
×10−2 mol, preferably lXl0−′ to 2×10−
'In moles': 2.;i・General formula [U) 47.・−°−z, −・1..

Zl is a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a tellurium azolium nucleus,
Represents an atomic group necessary to form a benzotellurazolium nucleus or a naphthobenzazolium nucleus, and these nuclei may have a substituent on a carbon atom. Specific examples of substituents include halogen atoms (e.g. fluorine atom, chloro atom, bromine atom), alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, butyl group, propyl group, etc.), and 4, an alkoxy group, a hydroxyl group, a nitro group, and the like. R21 and R22 represent a hydrogen atom, an alkyl group which may be monosubstituted, or an alkenyl group. Also R
21 and RZZ may form a bis structure via an alkylene group having 1 to 10 carbon atoms, or may form a carbocycle or a thioheterocycle.

X represents an anion. m represents 0 or 1, and m has a value of 0 when an inner salt is formed. Examples of anions represented by These include sulfate ions.

・Pap, bottom margin・';':::wo・' Next, typical examples of the compound represented by the above general formula [II] used in the present invention will be given.

[821 Ibi, Yujiji Geo 3)] (II)-1 Ct fl s [■]-2 ■ tHs (II)-3 nC5) 1z (n)-4 [■]-5 (lT]-6 CHtCH =Cth (n)-7 [■]-8 [■]-9 H3 (n)-10 (II) -11 (n)-12 C)IzCHgCHzSOs- ([) -13 (II)-14 [■] -15 CHgCII-CHz (II)-16 (U)-17 C112-(C1+□), -CIl□ (If)-19 (CL) tSO+-(CHz) xSOs-(n)-
20 HI (n)-21 CH.

(n)-22 ([]-23 (n)-24 The compounds represented by the general formula [Ding] of the present invention are, for example, JP-A-53-77616, JP-A-60-78444, JP-A-5
It can be synthesized as described in No. 8-50535 and the like.

The general formula (
The amount of compound TI) is 5X10- per mole of silver halide contained in the silver halide photographic material of the invention.
6 to 5 x 10-' moles, preferably 5xt
The silver halide photographic light-sensitive material of the present invention having an amount of 0-' to 5 x 10-'' moles 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 coated directly on the support or coated via a hydrophilic colloid layer that does not contain the silver halide emulsion, and a hydrophilic colloid layer is further applied as a protective layer on the silver halide emulsion layer. A colloidal layer may be applied, and the silver halide emulsion layer may be divided into silver halide emulsion layers of different sensitivities, e.g. high and low sensitivity.
In this case, the silver halide emulsion layer may be provided with an intermediate layer of a hydrophilic colloid layer between these layers, or an intermediate layer may be provided between the silver halide emulsion layer and the retention III layer. The layer containing the compound of general formula (1) and the compound of general formula [■] of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or the silver halide emulsion layer. is a hydrophilic colloid layer adjacent to the .

Further, as the silver halide that can be used in the present invention, for example, a type having a layered structure of at least two layers can be used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or conversely, silver bromide in the core and silver chloride in the shell. At this time, in order to make the hydrophilic colloid layer contain the compound of the general formula (II) of the present invention within 5 mol % of iodine in any layer, add the compound of the general formula (L[) to an appropriate water and/or organic solvent. There are two methods of adding the compound after dissolving it, or adding the solution after dissolving it in an organic solvent and dispersing it in a hydrophilic colloid matrix of gelatin or a gelatin derivative, or adding it after dispersing it in latex. , J-.7 The silver halide used in the silver halide photographic material of the present invention is preferably silver chlorobromide or silver chloroiodobromide containing at least 50 mol % of silver chloride. The average particle diameter of the silver halide grains used is preferably in the range of 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 2.
Adjust so that it becomes 0. The grain size of the silver halide grains used in the present invention is conveniently expressed by the edge length of the cubic grain, and the monodispersity S is calculated by dividing the standard deviation of the grain size by the average grain size 7 as shown in the following formula (i). Express the value by multiplying it by 100.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. The rhodium salt is preferably added at the time of grain formation, but it may also be added at the time of chemical W) formation or at the time of preparing the emulsion coating solution.

In this case, the rhodium salt may be a double salt as well as a simple salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The rhodium salt adder can be changed freely depending on the required sensitivity and gradation, but it is 10-8 mol to 1 mol to 1 mol.
The O-6 mole range is particularly useful.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts are often used for positioning purposes with high-light properties, ranging from 10 to 10 moles per mole of silver.
The silver halide used in the present invention, which is preferably in the range of 0 to 6 moles, can be spectral sensitized with the compound of general formula [1] and can also be sensitized with various chemical sensitizers. Examples of exacerbating agents include activated gelatin, sulfuric acid exacerbating agents (
Sodium thiosulfate, ruthiolubamide, thiourea, allylisothiacyane-1, etc.) Selenium sensitizers (N, N-
dimethylselenourea, selenourea, etc.) reduction sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooleite, curlate, 2-ourosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chlorobratate, etc. Various noble metal sensitizers represented by ester, sodium chloroparadite, etc. can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The spectrally sensitized silver halide and the compound represented by the general formula [II] used in the present invention are made to exist in the hydrophilic colloid layer, and hydrophilic colloids particularly advantageously used in the present invention include: Gelatin is preferred, and hydrophilic colloids other than gelatin include, for example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, and gelatin derivatives. , such as phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin, as described in U.S. Pat. No. 2,614,928, U.S. Pat. No. .520, No. 2.831, 76
Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in each specification of No. 7. These hydrophilic colloids form a silver halide-free layer,
For example, it can be applied to antihalation layers, protective layers, intermediate layers, etc.

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, and polystyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

The light-sensitive material according to the present invention contains a compound represented by the general formula [II] of the present invention in a hydrophilic colloid layer including at least one silver halide emulsion layer on a support as described above, for example. However, it has a structure in which a hydrophilic colloid layer of an appropriate thickness, preferably 0.1 to 10 μm, particularly preferably 0.8 to 2 μm, is coated as a protective layer on the silver halide emulsion layer. It is particularly preferable.

The silver halide emulsion layer and hydrophilic colloid layer used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, anti-oxidants, etc., as necessary. A staining agent, a pH adjuster, an antioxidant, an antistatic agent, a thickener, a granularity improver, a dye, a mordant, a brightener, a development speed adjuster, a matting agent, etc., within a range that does not impair the effects of the present invention. Can be used within.

Among the various additives mentioned above, those that can be particularly preferably used in the present invention include thickeners and plasticizers, such as those described in U.S. Patent No. 2,960,404;
Publication No. 39, West German Application Publication No. 1, 904, 604
specification, JP-A No. 48-63715, JP-A No. 45-1
Publication No. 5462, Belgian Patent No. 762,833,
US Patent No. 3.767.410, Belgian Patent No. 5
Substances described in the specifications of No. 58.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl Sulfone type, isocyanate type, sulfonic acid ester type,
Examples of hardening agents and ultraviolet absorbers such as carbodiimide, mucochloric acid, and acyloyl include US Pat. No. 3,253,921 and British Patent No. 1,309,349.
Compounds described in each specification etc. of No. 2, especially 2-(2
'-Hydroxy-5-tertiary butylphenyl)penztriazole, 2-(2-hydroxy-3,5-di-tertiary butylphenyl)hencytriazole, 2-(2-hydroxy-3-tertiary butyl-5- butylphenyl)-5-
Chlorbenzotriazole, 2-(2-hydroxy-3
Examples include ゜5-', -tertiary butylbutylphenyl benzotriazole, etc., and as dyes, U.S. Patent No. 2.072.908 and Narrow Patent No. 107
．． No. 990, U.S. Pat. No. 3,048,487, U.S. Pat. It may also be included. Furthermore, coating aids,
Emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent No. 548,
No. 532, L22L980, U.S. Patent No. 2,99
2.101, Patent No. 2,956,884, French Painting Patent No. 1,395,544, Japanese Patent Publication No. 48-431
Compounds described in Publication No. 25 etc. are preferred, especially those with 0.
Silica gel with a particle size of 5-20 μm, 0.5-20 μm
Examples include polymers of polymethyl methacrylate having a particle size of m.

The silver halide photographic material containing the compound of the general formula (II) of the present invention in the silver halide emulsion layer and/or other hydrophilic colloid layer can be used in the presence of a compound represented by the following general formula Cm]. Developing is preferred.

[In the formula, R31 is a 5- or 6-position nitro group, R3
□ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion. ] As a specific compound represented by general formula CIII), 5-
Examples include nitroindazole and 6-nitroindazole, but the present invention is not limited thereto in any way.

A compound represented by the general formula CI It may be added to the liquid or may be added as is.

The compound represented by the general formula [l11) is contained in a concentration range of preferably about 1 mg to 1,000 mg, more preferably about 50 mg to 300 mg, per developer 11.

Examples of the developing agent for the silver halide photographic light-sensitive material of the present invention, particularly for 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-mentioned general formula (fir).

HO÷C)l=CI+1-OH type developing agents include hydroquinone, and others include catechol, pyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, 2.5-dimethylhydroquinone, 2.3-dibromohydroquinone, 2.5-dihydroxyacetophenone, 2.5-diethylhydroquinone, 2.5-di-
p-Phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4- (2-hydroxy Benzoyl) pyrogallol, ascorbic acid sorta, etc.

Typical HO-(-C)I=CH+1-NH type developers include ortho and para aminophenols or aminopyrazolones, such as 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-amino-
2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, 2.4-
Cyamylsorcinol, 2,4.6-)riaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc. be.

Further, examples of H.zN+C=C+=NHt type developers include 4-amino-2-methyl-N, N-diethylaniline, 2.4-diamino-NN-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-N-n-sulfobutylaniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl,
Examples include 1.2°3.4-tetrahydroquinone.

Petrocyclic type 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-dimethyl-3-pyrazolidone. -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Pyrazolidones, l-phenyl-4-amino-5-pyrazolone, 1-(P-aminophenyl)-3-amino-
Examples include 2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, and 5-aminouracil.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess+Fourth Edition) No. 29
pp. 1-334 and Journal of the American
Chemical Society (Journal of the
American Chemical 5ociet
y) Developers such as those described in Vol. 73, p. 3.100 (1951) can be effectively used in the silver halide photographic material of the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as potassium sulfite or ammonium sulfite is used as a preservative in the developer used for processing the photosensitive material of the present invention, the effects of the present invention will not be impaired, and the effects of the present invention will not be impaired. This can be cited as one feature.

Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, it is necessary to adjust the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers, and provide a buffer function, as well as inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, and ethylenediaminetetraacetic acid, etc. Metal ion scavenger, methanol, ethanol, benzyl alcohol, development accelerator such as polyalkylene oxide, sodium alkylaryl sulfonate, natural saponin,
IJ! It is optional to add surfactants such as alkyl esters of the above-mentioned compounds or the above-mentioned compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, and ionic strength regulators such as sodium sulfate.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamines mentioned above include triethanolamine jetanolamine, ethanolamine trimethylamine 2-diethylamino-1-ethanol 2-methylamino-1-ethanol 3-distylamino-1-propanediol 3-diethylamine-1-propanol 5 -Amino-1-pentanoldiethylamine methylamine triethylamine dipropylamine di-isopropylamine 3.3'-diaminodipropylamine 3-dimethylamine-1-propatolhydantoic acid allylamine ethylamine dimethylamine ethylenediamine 2-dimethylaminoethanol 2 -ethylaminoethanol 2-(2-aminoethylamino)ethanoltetramethylammonium acetatecholinecholine chloridehydroxylamine sulfate 2-((2-aminoethylamino)-ethylaminetwoethanolaminoguanidine sulfate 6-aminehexanoic acid 3-amino -1-propatur 1-dimethylamino-2-propatul 2-hydroxy-4-thiadodecyltrimethylammonium (pea) pyridine glycine 0-aminobenzoic acid polyethyleneimine L-(+) -cystine hydrochloride benzylamine 2-amino -1-ethanol 4-amino-1-butanol 3-(dimethylamino)-1,2-propanediol 3-morpholino-1,2-propanediol 1,4-piperazinebis(ethanesulfonic acid)3-piperidino-1
, 2-propanediol, N-piperidine ethanol, and the like.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g per 11 of the developer, preferably 2
It is 0-200g.

Are these available? 8 medium can be used alone or in combination.

The silver halide photographic material of the present invention has excellent storage stability when developed using a developer containing the above-mentioned development inhibitor. Photosensitive properties can be obtained.

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

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably around 30°C, and the development time is generally completed within 3 minutes.
Particularly preferably within 40 seconds often brings about good results. Furthermore, it is optional to employ treatment steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-feeding, neutralization, etc., and these can be omitted as appropriate. Furthermore, these treatments may be so-called senmen image treatments 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 the following solutions A, B, and C.

Ku? Solution A〉 Ossein gelatin 17 g Polyisopropylene-polyethylene oxydisuccinic acid ester sodium salt 5 mj 210% ethanol solution Distilled water 1280 cc Solution B〉 Nitric acid 1! 170 g (
Distilled water 410 mff1 Solution C> Sodium chloride 40.9 g Potassium bromide 35.7 g Polyisopropylene oxydisuccinate ester sodium salt 10
% ethanol solution 3ml ossein gelatin
11 g distilled water
After keeping the 407mβ solution A at the solution temperature, the EAg value was 16.
Sodium chloride was added so that the concentration was 0 mv.

Next, solutions B and C were added by a double jet method using the mixer described in JP-A-57-92523 and JP-A-57-92524.

As shown in Table 1, addition was carried out by gradually increasing the addition flow rate over a total addition time of 80 minutes while keeping the EAg constant.

The EAg value was 3 ml/5 minutes after the start of addition from 160 mv.
EAg value of 120 m using β sodium chloride aqueous solution
v and maintained this value thereafter until the completion of mixing.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol/2 aqueous sodium chloride solution.

, 4-゛ or less margins 1-2゛Table 1 A metal silver electrode and a double-junction type saturated A g /A g Cβ reference electrode were used to measure the EAg value (the configuration of the electrode is as described in JP-A-57 The double junction disclosed in No.-197534 was used.)

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

Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system.

Also, during the addition, the pH value of the system was kept constant at 3.0.
% nitric acid aqueous solution.

After addition of liquids B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then desalted and washed with water in a conventional manner.
After adding 600 mff of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) and dispersing it by stirring at 55°C for 30 minutes, it was made into a 750 cc steel vessel.

Next, this emulsion was subjected to gold-sulfur enrichment, and 6-methyl-4-hydroxy-1,3,3a was added as a stabilizer.

7-Chitrazaindene was added. The emulsion was divided and as shown in Table 2, the compound of general formula (1) according to the present invention or the sensitizing dyes (CI) -(a) to (
f) ) 3 Xl0-' mol 1 mol Ag is added, n-
Sodium dodecylbenzenesulfonate 600mg/
A g 1 mol, 2-phenyl-3,5-di(p-methylphenyl)tetradurium chloride 600 mg/A
g 1 mol, styrene-maleic acid copolymer 2 g/A
1 mol of Ag was added and coated on a polyethylene terephthalate film so that Ag was 3.5 g and gelatin M was 20 g/rd. At this time, 1-decyl-2-(3-isopentyl)succinate 2-sodium sulfonate was added as a spreading agent at 30 mg/tri to make the amount of gelatin 1.0 g/tri.
A dura protective layer containing 25 mg/m of formalin as a hardening agent was applied in multiple layers.

(・'Margin below') □, -'・- and -' Comparative sensitizing dye (1) -(e) Table 2 Take three pieces of each of the obtained samples, and use a sensitometer to test one piece with an optical wedge. The other piece was exposed to contact screen 100N No. 2 (150L) manufactured by Dainippon Screen Mfg. Co., Ltd.
) was used to expose the shaded areas to xenon light. Also,
The remaining piece was subjected to the following processing without being exposed to light.

The above sample piece was processed in an automatic developing machine with a developing tank capacity of 401 using a developer having the following formulation and a commercially available fixer.

[Development processing conditions]

(Process) (Temperature) (Time) Development 28℃
Fixing for 30 seconds Washing at 28°C for 20 seconds Drying at 20°C for 20 seconds 20 seconds at 40°C [Developer composition] (Composition A) (Composition) When using the developer, dissolve the above composition A in the order of the composition in 500 ml of pure water, 17! It was finished and used.

For development method samples that were subjected to wedge exposure, draw a photographic characteristic curve and calculate the sensitivity at an optical density of 2.5 for sample N.
The relative value is calculated based on o, 1, and gamma is the optical density of 1.
．． The janθ values of the straight line portion from 0 to 2.5 are shown.

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

For dot quality, for so-called 50% dots where the area of the halftone area and the clear area are equal, the state of the fringe (blur) that occurs around the halftone dot is visually judged, and the smaller fringe is evaluated as 5.
Evaluation was made on a five-point scale.

That is, "5" is excellent, and "1" is extremely bad. If the 50% dot quality is less than "3", this is generally unacceptable.

In addition, for samples processed without exposure, 4 films were stacked and the residual color of the film was visually evaluated and evaluated on a 5-point scale, with "5" being colorless and "1" being a strong orange residual color. Indicated.

For general plate making, residual color below "3" is at a level that is considered a major drawback.

These results are shown in Table 3.

'1T゛Table 3 J'f It is higher than the sample (12 to 18.80 or less), and the gamma is extremely sharp at 16 to 20, and both the dot quality rank and residual color rank are superior to the comparison sample. , it can be seen that the sample has little residual color.

〔Effect of the invention〕

As mentioned above (the silver halide photographic light-sensitive material of the present invention is
Extremely high contrast can be obtained by rapid development using a conventional developer with high photosensitivity and high monosulfite ion concentration, and the effect is that dye staining after processing is extremely low.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Takatsuki Toru Proceedings (voluntary) August 12, 1988 Patent Application No. 109017 2, Name of invention Spectrally sensitized silver halide photographic light-sensitive material 3, Amendment person case and Relationship Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. FAX 03
(221) 19245, date of amendment order Vol. 6, amendment vs.
VI.

(1) In the specification, "sulfamide group" from the second line to the bottom line is corrected to "sulfamoyl group."

(2) "Alkylsulfonyl group" on page 3, lines 3 to 4 is corrected to "sulfoalkyl group."

(3) “(Moro) 7 Sun (Tan 2) 7” on page 15, line 14 of the same
＋ CI+2→, O-e CII#-A
” and correct it.

(4) On page 15, line 16, "sulfonamide group" is corrected to "sulfamoyl group."

(5) “Sulfoamide group,” on page 18, lines 3 and 4,
" is corrected to [sulfamoyl group,"].

(6) "Sulfonamide group" on page 18, line 8 and lines 9 to 10 of the same page is corrected to "sulfamoyl group."

(7) "(For example, N-methylsulfonamide group, N,N-dimethylsulfonamide group, etc.)" in the same page 18, lines 10 to 11 is replaced with "(For example, N-methylsulfamoyl group,
(N,N-dimethylsulfamoyl group, etc.)".

(8) "Alkylsulfonic acid group, sulfonic acid group," on page 19, lines 2 to 3, is corrected to "sulfoalkyl group, sulfo group."

(8) The structural formula of r (1)-(a)J on page 73 of the same is corrected as follows.

that's all

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a support and a hydrophilic colloid layer coated on the support and including at least one silver halide emulsion layer, wherein the hydrophilic colloid layer contains: 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 [II]. Photographic material. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z represents a group of nonmetallic atoms necessary to form an oxazole nucleus, benzoxazole nucleus, or naphthoxazole nucleus. R^1 represents an unsubstituted or substituted alkyl group. R^2 is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group,
Represents a carbamoylalkyl group, hydroxyphenyl group, hydroxyalkylphenyl group, phenyl group, alkoxyalkyl group, or a substituent -(CH_2)-_nA or -(CH_2)-_nO-(CH_2)-_nA. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfamide group, an alkylsulfonylamino group, or 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, an alkylsulfonyl group, a sulfo group, a chlorine atom, a fluorine atom, or a carboxy group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Z represents the atomic group required to form a thiazole, selenazole, or tellurium azolium ring. R^2^1
, R^2^2 represents a hydrogen atom, an optionally substituted alkyl group, or an alkenyl group. X^- represents an anion. m represents 0 or 1, and when an inner salt is formed, m
has a value of 0. ]