JPS62265648A - 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 particles in hydrophilic colloidal layers including a silver halide emulsion layer formed on a support 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 a silver halide emulsion layer formed on a support 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 oxazole, benzoxazole or naphthoxazole ring, R<1> is alkyl, R<2> is alkoxycarbonyl 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, X is H or acetyl and each of R11-R14 is H, alkyl, alkoxycarboxyl or aryl.

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 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 0.5μ
Silver halide consisting of a silver chlorobromide or silver chloroiodide emulsion with fine grains of m or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 mol% or more. A method is known in which a high-contrast halftone dot image or line image is obtained by processing a photosensitive material with an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions.

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-line 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. This lithium-type silver halide photographic light-sensitive material is produced using a conventional developer with a high concentration of sulfite ions.
For example, even if processed with a commercially available developing solution for photographic paper, the gamma is only 5 or 6, and fringes, which must be avoided in halftone dot formation, occur frequently. It is said that combination with mold developer is essential. Regarding this lithium type developer, please refer to G.I.
Journal of the Franklin Institute (J, A, CYule)
: J.Franklin In5titut
), Vol. 239, p. 221 (1945), which essentially contains only hydroquinone as a developing agent, and the concentration of sulfite ion, which acts as an antioxidant for the developing agent, is It is a low developer.

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 use in plate making are generally required to have so-called orthotype photosensitivity, which is photosensitivity in the green area.

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. 1,942.854, U.S. Patent No. 1,950,
No. 876, No. 1,957.869, No. 2,238,2
No. 31, No. 2,521.705, No. 2,647,05
No. 9, Special Publication No. 43-2606, No. 44-3644,
No. 46-18106, No. 46-18108, No. 48
-15032, 49-33782, 54-34
No. 252, No. 58-52574, U.S. Patent No. 2,839
, No. 403, No. 3,567.458, No. 3,625,
Examples include cyanine dyes and merocyanine dyes described in specifications such as No. 698.

[Problem that the invention seeks to solve]

These spectral enhancers not only increase the sensitivity in a specific wavelength range, but also have general properties such as (al) not being affected by other additives or affecting the effectiveness of the additive; ('b) Properties such as not causing changes in photographic characteristics such as a decrease in sensitivity or increase in fog over time, and (not causing dye staining after C1 processing) are required, but as mentioned above, When relatively quick development is performed,
Pigment staining after treatment becomes large, which is a big 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 highly soluble spectral enhancer 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.

Margin below.

c. Means for Solving Problems] As a result of various studies, the present inventors have developed a halogen halogen solution having a support and a hydrophilic colloid layer including at least one silver halide emulsion layer coated on the support. In the silver halide photographic light-sensitive material, the silver halide grains contained in the hydrophilic colloid layer are spectrally sensitized by a compound represented by the following general formula (1), and the hydrophilic colloid layer is 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 the compound represented by F).

General formula (I) z 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.), C1-C4 alkoxy group (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, etc. as the benzoxazole nucleus; 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6- Naphtho(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-)lifluoroethyl group, 2-(3-sulfopropyloxy)ethyl group , 2-(2-hydroxyethoxy)ethyl group, ethoxycarbonylethyl group, methylcarbinylethyl group, 2-sulfamoylethyl group, 2-carbamoylethyl group, 2-N,N-dimethyl as sulfamoylalkyl group carbamoylethyl group, phenethyl group, p-carboxyphenethyl group, sulfoaralkyl group such as p-sulfophenethyl group, 0-sulfophenethyl group, p-
Examples include hydroxyphenethyl group, allyl group, phenoxyethyl group, and the like.

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+CHz+iA or (mont), -
÷ (moh) represents voice. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfamide group, an alkylsulfonylamino group, or an alkoxy group having 1 to 8 carbon atoms,
n represents an integer value of 1-4.

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 RzO include alkoxycarbonylalkyl groups in which each alkyl group is substituted with a halogen atom (e.g., methoxycarbonylfluoromethyl group, ethoxycarbonylfluoromethyl group, fluoroethoxycarbonylethyl group, etc.), hydroxyalkyl M (Example x) hydroxyfluoroethyl group,
2-hydroxyfluoropropyl group, 3-hydroxyfluoropropyl group, 2,3-dihydroxyfluoropropyl group, etc.), hydroxyalkoxyalkyl group (e.g. hydroxymethoxyfluoromethyl group, 2-(2-hydroxyfluoroethoxy)ethyl group, -hydroxyfluoroethoxymethyl group, etc.), carbamoyl alkyl group (N-alkyl substitution, N,N-dialkyl substitution, N-hydroxyalkyl substitution, N-alkyl-N-hydroxyalkyl substitution, N,N-di(hydroxyalkyl) (including substituted carbamoyl alkyl groups and carbamoyl alkyl groups of 5- and 6-membered cyclic amines) (e.g., 2-carbamoylchloroethyl group, 2-N-(2-hydroxyethyl)carbamoylchloroethyl group, Ethylcarbamoylmethyl a, N S N-'
(2-hydroxyfluoroethyl)carbamoylmethyl group, 2-N,N-di(2-hydroxyethyl)carbamoylchloroethyl 5,N,N-dimethylcarbamoylchloromethyl group, cerphorinocarbamoylchloromethyl group, piperidine nocarbamoylmethyl group, etc.), hydroxyphenyl group, hydroxyalkylphenyl group having 7 to 9 carbon atoms (e.g. p-(2-hydroxyfluoroethyl)
phenyl M, m-(1-hydroxyfluoroethyl) phenyl group, etc.), or a substituent +CHz+iA or -(-C1l!- 纷0 + CH, +i-A. Here, A represents a nitrile group, an alkylsulfonyl group,
It represents a sulfamide group, an alkylsulfonylamino 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, a methylsulfonyl group, an ethylsulfonyl group, etc.), The sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms (for example, N-methylsulfonamide group, N,N-dimethylsulfonamide group, etc.), and the alkylsulfonylamino group is preferably one having 1 to 4 carbon atoms. The lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.).

n represents an integer value of 1-4.

R3 and R4 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably one with 1 to 4 carbon atoms, such as a methyl group or an ethyl group), or an alkoxy group (preferably one with 1 to 4 carbon atoms). , for example, a methoxy group, an ethoxy group), an alkylsulfonic acid group, a sulfonic acid group, a chlorine atom, a fluorine 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 (1) 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) -2 (1)-70CRcoSO,Na (I)-10 (I)-12 CI)-13 CIhSO! K (I)-14 (I)-15 CI) -1700Hz H3 (I] -22 (I)-27 CI)-28 (1]-29 (CHz) *SOJ (I)-30 (f)-34 (IL-35 (I)-36 CI)-37 CH, So, the compound represented by the above general formula (1) used in the present invention is disclosed in Japanese Patent Publication Nos. 46-549 and 46-18105.
No. 46-18106, No. 46-18108, No. 47-4085, No. 5B-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 [I] 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, halogenated S! 10-S per mole
~2x104 mol, preferably lXl0-' ~2X10
−'Mole.

General formula (II) Disturbance.

In the formula, X represents a hydrogen atom or an acetyl group.

and may be the same or different.

The acetyl group represented by X in general formula (n) also includes substituted acetyl groups. For example, it may be an acetyl group substituted with an alkyl group (methyl group, ethyl group, etc.), but it is preferable that X is a hydrogen atom.

Examples of the aryl group represented by R in formula (n) include phenyl, naphthyl, tolyl, and xyl, with phenyl being particularly preferred. These groups also include substituted groups. For example, halogen atoms (chlorine, bromine, etc.), alkyl groups (methyl, ethyl, propyl, etc.), alkoxy groups (methoxy, ethoxy, etc.), sulfonyl groups, amide groups (
It may also be an aryl group substituted with a methylamide group, an ethylamide group, etc.).

RIL+ R1□+RI3 and RI4 of general formula (II)
The alkyl group represented by is preferably an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.), and these alkyl groups also include substituted ones, such as hydroxyl group. group, amino group,
May be substituted with an acyloxy group etc., and
As the aryl group, a phenyl group, a naphthyl group, a xylyl group, a tolyl group, etc. can be used, but a phenyl group is particularly preferred, and these groups include substituted ones, such as halogen atoms (chlorine atoms, (bromine atom, etc.), an alkyl group (methyl group, ethyl group, propyl group, etc.), an alkoxy group (hydroxy group, methoxy group, ethoxy group, etc.), or the like. Examples of alkoxycarboxyl groups include methoxycarboxyl groups and ethoxycarboxyl groups, and these groups may be substituted with phenyl groups, hexenyl groups, and the like.

Further, specific examples of the compound represented by the general formula (n) are shown below, but the present invention is not limited to these compounds.

II-I IF-2CHI2■-
5 II -7CH3 CHI ll-9CHI If-6CHI CHI 11-8 CII*0H II-10CH3 QC) I! n −15, n −1 H II-17GHz II-18CJt ) CI(.

H3 If-19II-20 n -21m -22 If -23 II -24 C.I.

II -25If -26 CI 0CHsIf
-27II -28 SOJ NHCOCHs
OC O H9! [-31II ■-33 ■-35 ■-34 ■-37 ■-39 ■-38 Hs CI.

II -43n -44 I n -45II -46 Cj! The compound represented by the general formula (n) of the present invention is, for example,
It can be synthesized as described in No. mss-sos3s.

1C formula (
The amount of the compound I[] is 5X10 per 1!1 mole of halide contained in the silver halide photographic light-sensitive material of the invention.
-'' to 5XIO-' mole range is preferred, and more preferably 5X
The range is preferably from 10-' to 1X10-' moles.

The silver halide photographic 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, and this silver halide emulsion is directly coated on the support. It may be coated or coated via a hydrophilic colloid layer that does not contain a silver halide emulsion, and a hydrophilic colloid layer may be further coated as a protective layer on the core silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, e.g. high and low sensitivity, in which case the silver halide emulsion layer has a hydrophilic layer between the layers. An intermediate layer of the sexual colloid layer may be provided, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. The layer containing the compound is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

In order to incorporate the compound of the general formula (n) of the present invention into the hydrophilic colloid layer, the compound of the general formula (II) is dissolved in appropriate water and/or an organic solvent and added, or dissolved in an organic solvent. Examples include a method in which a 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 added after being dispersed in latex.

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.
The grain size of the silver halide grains used in the present invention is conveniently expressed by the principal dimension of cubic grains, and the monodispersity S is calculated by averaging the standard deviation of the grain size as shown in formula (1) below. It is expressed as a value obtained by dividing the value divided by the particle size Y and multiplying it by 100.

Further, as the silver halide that can be used 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 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, iodine can be contained in any layer within 5 mol%.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening 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 amount of rhodium salt added can be freely changed depending on the required sensitivity and gradation, but from 1O-1 mole to 1 mole per 11 moles.
A range of 0.04 moles 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 high-light properties, ranging from 101 to 1 mole per mole of silver.
It can be preferably used up to a range of 0.04 mol.

The silver halide used in the present invention has the general formula (1)
In addition to spectral sensitization using the compounds described above, sensitization can be performed using various chemical sensitizers. Examples of sensitizers include activated gelatin, sulfuric acid sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction Sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooleite, potassium aurothiocyanate, potassium chlorooleate,
2-Aurosulfobenzothiazole methyl chloride,
Various noble metal sensitizers represented by ammonium chloroparadate, potassium chlorooleate, 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, for example, a compound represented by the general formula (n) of the present invention in a hydrophilic colloid layer including at least one silver halide emulsion layer on a support as described above. 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 the lignophilic colloid layer used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, Anti-stain agents, p) (modifiers, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, capping agents, etc.) may impair the effects of the present invention. It can be used within the specified range.

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. Pat.
Publication No. 39, West German Application Publication No. 1.904.604, Japanese Patent Publication No. 48-63715, Japanese Patent Publication No. 45-154
No. 62, Belgian Patent No. 762.833, U.S. Patent No. 3,767,410, Belgian Patent No. 558
．． Substances described in the specifications of No. 143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based , isocyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, acyloyl-based and other hardening agents, and ultraviolet absorbers include, for example, U.S. Patent No. 3.
253.921 and British Patent No. 1.309.349, especially 2-(2'-
hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3-tertiary butyl-5-butylphenyl) )-5-chlorobenzotriazole, 2-(2-hydroxy-3°5-di-tertiary butylphenyl)-5-chlorobenzotriazole, etc.; .908, Narrow Patent No. 107.9
No. 90, U.S. Pat. No. 3,048,487, U.S. Pat. In addition, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include: Patent No. 548.53
No. 2, No. 1,221.980, U.S. Patent No. 2.99
Specifications of No. 2.101, No. 2.956.884, Buddhist Temple Patent No. 1.395.544, Special Publication No. 1973-431
Compounds described in Publication No. 25 etc. are preferred, especially those with 0.
Silica gel with particle size of 5-20pm, 0.5-20μ
Examples include polymers of polymethyl methacrylate having a particle size of m.

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

[In the formula, R3+ is a 5- or 6-position nitro group, R3
□ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. 5-
Examples include nitroindazole and 6-nitrointasole, but the present invention is not limited thereto in any way.

The compound represented by the general formula (I[I) can be dissolved in organic solvents such as diethylene glycol, triethylene glycol, ethanol, jetanolamine and triethanolamine, alkalis such as sodium hydroxide, acids such as acetic acid, etc. It may be added to the developer or may be added as is.

The compound represented by general formula (III) 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 (II[).

Typical HO÷CH=CH-h-OR type developing agents include hydroquinone, as well as catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, and 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-phenylcatechol,
Examples include 3-methoxy-catechol, 4-acetyl-pyrogallol, 4-(2-hydroxybenzoyl)pyrogallol, and sodium ascorbic acid.

In addition, as a HO÷CB-CI+TNH2 type developer,
Ortho and rose aminophenols or aminopyrazolones are representative, including 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-amino-2-phenyl Phenol, 3,4-diaminophenol, 3-methyl-4,6-riaminophenol, 2,4-cyamylsorcinol, 2,4.6-)riaminophenol, N-
Examples include methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol.

Furthermore, HzN + C=C + TN Hz type developer color 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-N-n-sulfobutyl Aniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl, l,
Examples include 2゜3.4-tetrahydroquinone and 9-aminoylolidine.

Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-' hirazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 3 such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
-Pyrazolidones, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 5 - Aminouracil, etc. can be mentioned.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
an Chemical 5ociety) Volume 73,
3, p. 100 (1951) etc. can be effectively used in the silver halide photographic window optical 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,
It is optional to add surfactants such as saccharides or alkyl esters of the aforementioned 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-diethylamino-1-propanediol 3-diethylamino-1-propanol 5 -Amino-1-pentanoldiethylaminemethylaminetriethylaminedipropylaminedi-isopropylamine3.3'-diaminodipropylamine3-dimethylamino-1-propatolhydantoic acidallylamineethylaminedimethylamineethylenediamine2-dimethylaminoethanol2- Ethylaminoethanol 2-(2-aminoethylamino)ethanoltetramethylammonium acetatecholinecholine chloridehydroxylamine sulfate 2-((2-aminoethylamino)-ethylaminoco-ethanolaminoguanidine sulfate 6-aminohexanoic acid 3-amino-1 -Propatur 1-Dimethylamino-2-Propatur 2-Hydroxy-4-thiadodecyltrimethylammonium (pta) 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, 1.4-7'tanediol, 1,
Among them, diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g, preferably 20 to 200 g, per 11 of the developer.

These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention can be developed with a developer containing the above-mentioned development inhibitor, thereby obtaining photosensitive characteristics with extremely excellent storage stability.

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 processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called early field image processing such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕

A silver chlorobromide emulsion was prepared using the following solutions A, B, and C.

Solution A> Ossein gelatin 17 g Polyisopropylene-polyethyleneoxydisuccinate sodium salt 5% ethanol solution Distilled water 1280 cc Solution B> Silver nitrate 170 g Distilled water
410mj! <Solution C> Sodium chloride 40.9 g Potassium bromide 35.7 g Polyisopropylene oxydisuccinate sodium salt 10
% ethanol solution 3ml ossein gelatin
11 g distilled water
After keeping the 407mf 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 a using 1 of 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/l aqueous sodium chloride solution.

Table 1: For the measurement of EAg values, a metal silver electrode and a double junction saturated Ag/AgCβ reference electrode were 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.
Ossein gelatin aqueous solution 600ml! (containing 30 g of ossein gelatin) was added and dispersed by stirring at 55° C. for 30 minutes, and the volume was adjusted to 750 cc.

Next, this emulsion was subjected to sulfur-containing sensitization, and 6-methyl-4-hydroxy-L 3.3a was used 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 ((I) - (a) ~
(f) ) 3xto-' 1 mol Ag was added to each emulsion for dye sensitization, and compound (n) was added to each emulsion at 700 mg/A g 1 mol as shown in Table 2, and n-dodecylbenzenesulfone was added. Sodium acid 600mg/A
g 1 mol, 2.3. 600 mg/Ag 1 mol of 5-triphenyltetrazolium chloride and 2 g/Ag 1 mol of styrene-maleic acid copolymer were used. At that time, 30 mg/d of sodium 1-decyl-2-(3-isopentyl)succinate 2-sulfonate was added as a spreading agent and 25 mg/rd of formalin was included as a hardening agent so that the amount of gelatin was 1.0 g/rd. A dura protective layer was applied in multiple layers.

Comparative sensitizing dyes (1)-(d) (1)-(e) Table 2 Three pieces of each sample were taken, and one piece was exposed stepwise to tungsten light using a photosensitive needle and an optical wedge. The other piece was a contact screen GN No. 2 (150L) manufactured by Dainippon Screen Manufacturing Co., Ltd.
The shaded areas were exposed to xenon light. Further, the remaining piece was subjected to the following processing without being exposed to light.

The sample piece was processed using a developer having the following formulation and a commercially available fixer in an automatic developing machine with a developing tank capacity of 4 ON.

[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 40°C for 20 seconds [Developer composition] (Composition A) (Composition) When using the developer, add the above composition A,
They were dissolved in the order of their composition and finished to 11 for use.

For developed samples 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 tanO value of the linear section from 0 to 2.5 is 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.

Table 3 (Nl 1-11) has a relative sensitivity of 100 to 125, which is higher than comparative R (1'k12 to 18.80 or less).
The gamma is also extremely hard (m7) at 16 to 20, and both the dot quality rank and the residual color rank show superior values compared to the comparative samples, which indicates 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
It has the advantage that an extremely high contrast can be obtained by rapid development using a normal developer having high photosensitivity and a high concentration of sulfite ions, and there is extremely little dye staining after processing.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Toru Takatsuki Commissioner of the Patent Office Kuni Ogawa
Husband 1. Display of incident 1986 ¥ Patent side No. 109011 name (1
27) Konishiroku Photo Industry Co., Ltd. Dia Palace 506
No. FAX 03 (221) 19245, Date of amendment order Voluntary issue 6, Subject of amendment: ``Detailed description of the invention'' column in the description.

(1) In the specification, "sulfonamide 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) Page 15, line 14 (7) r (-e'Hz
)-S3-(÷z).

"Responsibility" to "±C1l□→, O+ C1l trA"
and correct it.

(4) Page 15, line 16 and page 18, lines 3 to 4,
"Sulfoamide group" in line 8 of the same page and lines 9 to 10 of the same page are respectively corrected to "sulfamoyl group."

(5) "N-methylsulfamide group" on page 18, line 10 of the same is corrected to "N-methylsulfamoyl group."

(6) "rN, N-dimethylsulfonamide group J G rN, N-dimethylsulfamoyl group" on page 18, lines 10 to 11.

(7) On page 19, lines 2 and 3, "alkyl sulfonic acid group" is corrected to "sulfoalkyl group."

(8) On page 19, line 3, "sulfonic acid group" is corrected to "sulfo group."

(9) The structural formula of r (1)-(a)'J on page 69 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] ▲There are 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 carbamoyl alkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a phenyl group, an 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 sulfonamido 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, X represents a hydrogen atom or an unsubstituted or substituted acetyl group. R_1_0 represents an unsubstituted or substituted aryl group. R_1_1, R_1_2, R_1_3, and R_1_4 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxycarboxyl group, or an unsubstituted or substituted aryl group, and each may be the same or different. ]