JPS61270745A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material high in photosensitivity and contrast, developing rapidly, and small in dye stains after processing by spectrally sensitizing silver halide grains with a specified merocyanine dye, and incorporating a specified tetraazolium compd. in a hydrophilic colloidal layer. CONSTITUTION:A photosensitive material suitable to a printing plate material, especially high in green-sensitivity and capable of rapidly developing a halftone dot image can be obtained by incorporating in a silver halide emulsion layer as a spectral sensitizer the merocyanine dye represented by formula I (Z is a nonmetallic atomic group necessary to form an oxazole, benzoxazole, or naphthoxazole ring; R<1> is an optionally subtd. alkyl; R<2> is dalkoxycarbonylalkyl, hyroxyalkyl, or the like or -(CH2)n-A, A is CN, alkylsulfonyl, or the like; n is 1-4; and R<3>, R<4> are each, optionally same or different, H, alkyl, Cl, or the like), and adding to the hydrophilic colloidal layer a compd. represented by formula II in which R<5>, R<6>, R<7> are each H or a group negative in Hammett's sigma value and all of them are not simultaneously H, and X is an anion.

Description

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

[Background of the invention]

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 the silver oxide grains is about 0.5
Silver halide photosensitive material consisting of a silver chlorobromide or silver chloroiodide emulsion with fine grains of p or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 moles or more. It is known to process the material with an alkaline developer containing only hydroquinone as a developing agent, with a low concentration of sulfite ions, to obtain halftone dot images or line images with higher contrast.

This type of silver halide photosensitive material is known as a Lisuya silver halide photosensitive material, and it 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 silver halide photographic light-sensitive material, photographing the original through a crossed S screen or a contact screen, and then using a so-called lithium silver halide photographic material, which has a very low concentration of sulfite ions and contains only a hydroquinone developing agent. A halftone image is formed by developing with a Lith type developer. This Lisuya silver halide photographic light-sensitive material is produced using a normal developer with a high concentration of sulfite ions.
For example, even when processed with a commercially available developing solution for photographic paper, the gamma is only 5 or 6, which is the most important thing to avoid when forming halftone dots;
For positive use, it is said that a combination with the above-mentioned Risuya Genrin liquid is essential. Regarding this squirrel-type developer, please refer to J.N.C.A.'s Journal of Oz the Franklin Institute (J.

A, CYule: J, Franklin In5t
rtute), Volume 239, Page 221 (1945'
) K is described in detail, and is essentially a developer solution containing only hydroquino/ as a developing agent and having a low concentration of sulfite ions that serve as an antioxidant for the developing agent.

Such developers have poor storage stability and are susceptible to auto-oxidation, so in order for plate makers to always obtain high-quality halftone negative or halftone positive images, K is a measure of 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 Lith development processing, in addition to managing the developer to keep the activity constant, there are two other problems: the processing speed is slow.
There are two major disadvantages.

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 discloses a silver halide photographic light-sensitive material containing a tetrazolium salt as a technique for obtaining extremely high-contrast images suitable for plate making using a developer with high stability. A method using the 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 orntive 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.

1,957,869, 2,238,231, λ521,705, 647,059, Special Publication No. 4
No. 3-2606, No. 44-3644, No. 46-181
No. 06, No. 46-18108, No. 48-15032
No. 49-33782, No. 54-34252, No. 58-52574, U.S. Patent No. 2,839,403,
Examples include cyanine dyes and methocyanine dyes described in specifications such as No. 3,567,458 and No. 3,625,698.

[Problem that the invention seeks to solve]

These spectral sensitizers have a general property, for example, of increasing the sensitivity in a specific wavelength range.

(1) It should not be affected by other additives or affect the effect of the additive. (2) It should not cause changes in photographic properties such as a decrease in sensitivity or an increase in capri even after time has passed. 3) Properties such as not causing dye staining after processing are required, but when the above-mentioned relatively rapid development is performed, dye staining after processing increases, which is a big problem in practice.

In order to reduce dye staining, K has a low staining property for hydrophilic colloids such as gelatin, and is easily leaked into the processing solution.
It is sufficient to use a spectral sensitizer with high solubility, and various compounds have been proposed in the past, but spectral sensitizers have a major influence on the development effect that provides the extremely high contrast required for plate making. It is difficult to apply methods for resolving dye stains in ordinary light-sensitive materials to silver halide photographic light-sensitive materials that undergo high dust resistance development, as problems such as a decrease in dust resistance often occur. .

The object of the present invention is to solve the above-mentioned problems, to obtain an extremely high contrast through a rapid development section 111c that has high photosensitivity and uses a normal developing solution with a high concentration of sulfite ions, and to prevent dye contamination after processing. The object of the present invention is to provide a photographic material having extremely low levels of Gl.

[Means of problem solving]

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

General formula [I] RO4 R3 Z represents an atomic group necessary to complete an oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus,
These nuclei may have substituents on carbon atoms.

Specific examples of substituents include /%9 gene atoms (e.g. furan atom, chlorine atom, bromine atom), unsubstituted furkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group). ), a flufoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, propoxy group, butoxy group), a hydroxy group, a flufoxy dicarbonyl group having 2 to 6 carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group) groups), alkylcarbonyloxy groups having 2 to 5 carbon atoms (e.g., 7 cetyloxy groups, propionyloxy groups, etc.), phenyl groups, hydroxyphenyl groups,
etc. can be mentioned.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, 4-phenyloxazole, etc. as the oxal nucleus; benzoxazole, 5- as the benzoxazole nucleus; I: I lohenzoxazole, 5-bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole,
5-7 Cetyloxypenzoxazole.

5-phenylbenzoxazole, 6-methylbenzoxazole, 6-medoxybenzoxazole, 5.6
-dimethylbenzoxazole, 6-riρ-5-methylbenzoxazole, etc., as naphthoxazole cores, naphtho[l・2-a)oxazole, naphtho[2・1
-d]oxazole, Nando[2,3-a]oxazole, and the like.

W represents an unsubstituted or substituted alkyl group.

Examples of substituents include zeta-doloxy 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 further includes sulfonate group). or a hydroxy group), a furkylsulfonyl group having 2 to 5 carbon atoms, a furkylsulfonyl group having 1 to 4 carbon atoms,
Sulfamoyl group, unsubstituted or substituted carbamoyl group (
(including a substituted carbamoyl group substituted with a furkyl group having 1 to 4 carbon atoms), a substituted phenyl group (examples of substituents include:
(sulfo group, carboxy group, human-oxy group, etc.), vinyl group, etc.

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-human aky7-3-sulfobutyl group, 2
- Clo-3-sulfoalkyl group, etc., 2-sulfonate ethyl group, 3-sulfonate propyl group, carboxyfulkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, 2,2,2-trifluoroethyl group , 2-(3-sulfobyloxy)ethyl group, 2-(2-human-oxyethoxy)ethyl group, ethoxycarbonylethyl group, methylsulfonylethyl group, 2-sulfoylfurkyl group, 2-sulfoylfurkyl group, 2, - Rubamoylethyl group, 2-N. -N
-dimethylcarbamoylethyl group, phenethyl group,
Examples of the p-hydroxyphenethyl group and sulfo7ralkyl group include p-sulfo7enethyl group, 0-sulfophenethyl group, p-hydroxyphenethyl group, heptadyl group, phenoxyethyl group, and the like.

The prefix is a flukoxyl group (e.g. methoxycarbonylmethyl group, ethoxycarbonylmethyl group,
Ethoxycarbonylethyl ft. ), hydroxyalkyl groups (e.g. 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2,3-ditoxibyl group, etc.), hydroxyalkoxyfurkyl groups (e.g. hydroxymethoxymethyl group, 2-(2-
(hydroxyethoxy)ethyl group, 2-hydroxyethoxymethyl group, etc.), carbamoylfurkyl group CN-alkyl substitution, N-N-difurkyl substitution, N-hydroxyfurkyl substitution, N-furkyl-N-hydroxyfurkyl substitution, N -N-di(hydroxyalkyl) 11i substituted carbamoyl alkyl groups and carbamoylfurkyl groups of 5- and 6-membered cyclic amines) (for example, 2-carbamoylethyl groups, 2-N-(2-hydroxy ethyl)carbamoylethyl group, N-hydroxyethylcarbamoylmethyl group, N-N-di(2-hydroxyethyl)carbamoylmethyl group, 2-N-N-di(2-hydroxyethyl)carbamoylethyl M, N-N- dimethylcarbamoylmethyl group, cellfolinolylbamoylmethyl group, biperidinoylbamoylmethyl group, etc.), hydroxyphenyl group, hydroxyfurkylphenyl a having 7 to 9 carbon atoms
p-(2-hydroxyethyl)phenyl ts,
m-(1-hydroxyethyl)phenyl group, etc.), or a substituent +CH2 +nA.

Human represents a nitrile group, an alkylsulfonyl group, a sulfone 7mido group, a furkylsulfonyl 7mino group, or a lower alkoxy group, among which the furkylsulfonyl group is
Preferably it is a furkylsulfonyl group having 1 to 4 carbon atoms (e.g. methylsulfonyl group, ethylsulfonyl group, etc.), and the sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms (e.g. N-methylsulfonyl group). amide group, N,N-dimethylsulfonamide group, etc.), and the alkylsulfonylamino group is preferably a furkylsulfonylamino group having 1 to 4 carbon atoms (e.g., methylsulfonyl group), The alkoxy group preferably has 1 to 4 carbon atoms (e.g. methoxy group,
ethoxy group, etc.).

W and W may be the same or different, and each hydrogen atom, a furkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, etc.), an alkoxy group having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, etc.) ), chlorine atom, or carboxy group.

Particularly preferred in the compound represented by the above general formula CI) is the case where W represents a straight chain or branched C1-4 furkyl group substituted with a sulfo group or a carboxyl group and/or a hydroxyl group, Specifically, sulfoethyl group, sulfobuyl 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) -1 (I: l -2 [Eng] -3oH [I] -5 H CI) -9. □ CI]-10C'H2C0NHCH2CH20H[:[
] -11 CI) -13CH2C0NHCH,CH20H■ CH20H■ [Engineering] -15CH2CH20CH2CH20H(I)-
160H (I) -170H 0M2CHCH20H CH3 CI] -18CH2CH2C0NH2 (1) -19CH2CO2C3H7 CI) -20CH2CH20CH3 CH2CH2802CH3 (i) -24 CH20H2ON (I) -25 ” -” CH 2CH2NH302CH3 [
■〕-” CH2CH2802NH
2(I)-32 (1)-33CH2CH2CH2802NH2CI)-
34CH2CH2802CHs1J) -36 CH*80sK The compound represented by the above general formula CII 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. 58-52574, U.S. Patent λ
No. 839,403, No. 1 & No. 384486, No. 3,625,698, No. 3,480,439, No. 3
．． It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 567.458 and the like.

The merocyanine dye represented by the general formula CI) used in the present invention can be added and dispersed in a silver halide emulsion by a conventionally known method. If you speak, Tokuko No. 49-44895, Tokukai No. 50-1
The method of dispersing and adding with a surfactant described in the specification of No. 1419, JP-A-53-16624, JP-A-53-16624;
102732, US Pat. No. 53-102733, US Pat. No. 3,469,987, and US Pat. No. 3,676.147.
Examples include the method of adding it as a solid solution as described in the specification of East German Patent No. 143,324. Other merocyanine dyes can be used in water-soluble solvents such as water, ethanol, methanol, acetone, n-prohanol, heptadated alcohol,
It may be dissolved in a solvent such as pyridine alone or in a mixed solvent thereof and added to the emulsion.

The odor can 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, 104 to 2X1 (1'1 mol, preferably 104 to 2X10) per silver halide emulsion. -3 moles.

Further, the merocyanine dye used in the present invention is, for example,
Special Publication No. 43-4933, No. 43-4936, No. 46
-1810? No. 46-1999, No. 47-111
No. 14, No. 48-1762, No. 48-38408,
K may be used in combination with other dyes disclosed in the specifications of US Pat. No. 56-38937, US Pat. No. 58-52574, US Pat. More intense color sensitization is possible.

In the present invention, substituents R1 and R2 of the phenyl group of the triphenyltetrazolium compound represented by the general formula (IT)
, Rs must have a negative Hammett's sigma value (σF) indicating a hydrogen atom or an electron-donating group, that is, an electron-donating group.

Hammett's sigma value for phenyl substitution has been reported in many publications, for example in the Journal of Medicinal Chemistry.
l Chemistry) Vol. 20, p. 304, 1977
Examples of groups with negative sigma values include the methyl group (σ, ==-Q, 17, hereinafter σν value), ethyl group (-0,15), cyclopropyl group (-0,21), n-propyl group (-0,13), lid,
. -bouvil group (-0,15), cyclobutyl group (-0
, 15), n-butyl group (-0,16), 1so-butyl group (-0,20), n-pentyl group (-0,15),
cyclohexyl group (-0,22), ami7 group (-0,6
6), 7 cetyl 7mi/group (-0,15), human-xyl group (-0,37), methoxy group (-0,27), ethoxy group (-0,24), p poxy group ( -0,25), butoxy group (-0,32), pentoxy group (-0,34)
etc., and all of these have the general formula (If
) is useful as a substituent for compounds.

Specific examples of compounds represented by the general formula CU used in the present invention will be given below, but the compounds of the present invention are not limited thereto.

(U) -1 The tetrazolium compound used in the present invention is, for example, chemical review
s) It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound of the present invention is used in an amount of about 1 to about 101, preferably about 10 to about 11, per mole of silver halide contained in the silver halide photographic light-sensitive material of the present invention. preferable.

The silver halide photographic material of the present invention comprises a support and at least one silver halide emulsion layer and at least one hydrophilic colloid layer coated on the support.
This silver halide emulsion layer is coated directly on the support or coated via a hydrophilic colloid layer that does not contain the silver halide emulsion, and the hydrophilic colloid layer is the silver halide emulsion layer. It may be coated as a protective layer on the support or between the support and the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, such as high and low sensitivity. In this case, the silver halide emulsion layer may have an intermediate layer of a hydrophilic colloid layer between these layers, or an intermediate layer between the silver halide emulsion layer and the protective layer. Good too. The layer containing the tetrazolium compound of the present invention is a silver halide emulsion layer and/or the various hydrophilic colloid layers described above.

In the most preferred embodiment of the present invention, the tetrazolium compound of the present invention is contained in a silver halide emulsion layer, and the hydrophilic colloid contained in the silver halide emulsion layer and the hydrophilic fluid layer is gelatin or a gelatin derivative. It is a silver oxide photographic material.

K, which is used to incorporate the tetrazolium compound of the present invention into the silver halide emulsion layer and/or hydrophilic colloid layer, can be added by dissolving the tetrazolium compound in appropriate water and an organic solvent, or by adding a solution dissolved in an organic solvent. Examples include a method in which the agent is added after being dispersed in a hydrophilic colloid matrix such as gelatin or a gelatin derivative, or a method in which the agent is added after being dispersed in latex. The present invention may use any of these methods.

The tetrazolium compound used in the present invention can be used alone to obtain preferable image characteristics. Further, even if these tetrazolium compounds are used in combination of 281 or more in an appropriate ratio, the image characteristics will not be adversely affected. Furthermore, the tetrazolium compound of the present invention and the tetrazolium compound other than the present invention may be used in an appropriate ratio.

One preferred embodiment of the present invention is to add the tetrazolium compound according to the present invention to a silver halide emulsion layer. In another preferred embodiment of the present invention, the hydrophilic fluid is added to a hydrophilic colloid layer directly adjacent to a hydrophilic colloid layer containing a silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer. .

In another embodiment, the tetrazolium compound according to the invention may be dissolved in a suitable organic solvent such as methanol, ethyl alcohol, etc.
It is dissolved in alcohols such as alcohol, ethers, esters, etc. and applied directly to the outermost layer on the silver halide emulsion layer side of the silver halide photographic light-sensitive material using the over-coating method. ... May be included in silver halide photographic materials.

In the present invention, 7 binds to the tetrazolium compound of the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention.
Particularly favorable results can be obtained when ion is used in combination. Examples of such 7-ions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, specifically p-)luenesulfonic acid anions, etc. Lower flukylbenzenesulfonic acid 7-ions, p-dodecylbenzenesulfonic acid 7-ions, flukylnaphthalenesulfonic acid 7-ions, lauryl sulfate 7-ions, tetraphenylporones, di-2-
Cyfurkylsul 7-osuccinate 7-ions such as ethylhexyl sulfosuccinate 7-ions, polyether alcohol sulfate 7-ions such as cetyl polyethenoxysal 7-ate anions, stearic acid 7-ions, etc.
Examples include polyacrylic acid 7-ions.

Such 7-ion may be added to the hydrophilic colloid layer after being mixed in advance with the tetrazolium compound of the present invention, or it may be added alone to the silver halide emulsion layer containing or not containing the tetrazolium of the present invention or to the hydrophilic colloid layer. It can be added to the sexual colloid layer.

The silver halide used in the silver halide photographic material of the present invention is AgC1! /AgBr ratio is 10010
Silver chlorobromide of 2/9B to 2/9B is preferable, AgCE△g
Particularly preferred is one having a Br ratio of 90/10 to 50,150.

In addition, the average grain size of silver halide grains is 0.10 μm to 0.
．． 40 μm, and the coefficient of variation of the particle size distribution expressed as (standard deviation of particle size distribution)/(average particle size) x 100 is 1.
A monodisperse type of 5% or less is preferable.

The silver halide used in the present invention can be sensitized with various chemical sensitizers. As a sensitizer,
For example, activated gelatin, sulfuric acid sensitizer (sodium thiosulfate, 7
lylthiocarbamide, thiourea, allyl isothiacyanate, etc.) selenium sensitizers (N,N-dimethylselenourea, selenouria 1%) reduction sensitizers (triethylenetetramine, stannic chloride, etc.), e.g. Various noble metal sensitizers such as oleite, potassium autothiocyanate, potassium chlorooleate, 2-oresulfobenzothiazole methyl chloride, ammonium flurovaladate, potassium chlorooleate, sodium chloroparadite, etc. Each can be used alone or in combination of two or more. When using a metal sensitizer, p-danmon can also be used as an auxiliary agent.

The spectrally sensitized silver halide and tetrazolium compounds according to the invention are present in a hydrophilic colloid layer, and the hydrophilic colloid particularly advantageously used in the invention is gelatin; Colloids include, for example, colloidal fulpmin, agar, 7Rabi 7 gum, alginic acid, hydrolyzed cellulose acetate, acrylic 7mide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate,
Gelatin derivatives, such as U.S. Pat. No. 4,614,928;
phenylcarbamyl gelatin, heptasylated gelatin as described in each specification of the same No. 2,525,753,
Phthalated gelatin, or U.S. Patent No. 2.548,5
No. 20 and No. 2,831,767, polymerizable monomers having ethylene groups such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester are added to gelatin. Examples include those obtained by graft polymerization, and these hydrophilic colloids can also be applied to layers that do not contain silver halide, such as halide carbon prevention layers, protective layers, and intermediate layers.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Typical examples include cellulose acetate, 7 lb G+-snitrate, polyester films such as polyethylene terephthalate, poly7mid film, polypropylene film, polycarbonate film, polystyrene film, and the like. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

The photosensitive material according to the present invention comprises a hydrophilic 7241 silver halide emulsion layer comprising at least one silver halide emulsion layer on the support as described above.
The layer contains the tetrazolium compound of the present invention, and the layer has an appropriate thickness on the silver halide emulsion layer, preferably 0.1 to 10 μm, particularly preferably 0.8 to 2 μm.
It is particularly preferable to have a structure in which a hydrophilic fluid layer of m is coated as a protective layer.

The silver emulsion layer and hydrophilic fluid layer used in the present invention contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, and ultraviolet absorbers, as necessary. , antistaining agents, PH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed adjusters, matting agents, etc. that may impair the effects of the present invention. It can be used within a certain range.

Among the various additives mentioned above, those that can be preferably used in the present invention include thickeners and plasticizers, such as those described in U.S. Pat.
Publication No. 939, West German Application Publication No. 1,904,604, Japanese Unexamined Patent Publication No. 48-63715, Japanese Patent Publication No. 45-15
No. 462, Belgian Patent No. 762,833, U.S. Patent No. 3.76-7.410, Belgian Patent No. 5
Examples of hardening agents include aldehyde-based, epoxy-based, ethyleneimine-based, and active haptics, such as styrene-maleic acid undercopolymer, dextran sulfate, etc. type, vinyl sulfone type, inrefnate type, sulfonic acid ester type,
Examples of various hardening agents and ultraviolet absorbers such as carbodiimide, mucochloric acid, and acyloyl-based agents include U.S. Patent No. 3,253,921 and British Patent No. 1,309.349.
Compounds described in each specification etc. of No. 2, especially 2-(
21-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3゜5-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3-tertiary butyl- 5-butylphenyl)-5-
Coolbenzotriazole, 2-(2-hydroxy-3
, 5-di-tertiary butylphenyl)-5-chlorobenzotriazole, etc., and as dyes,
U.S. Patent No. 2,072,908, Strong Country Patent No. 107,
No. 990, US Pat. No. 3,048,487, US Pat. You can force me. British Patent No. 548,5 is used as a surfactant used to control various physical properties of photosensitive materials, coating aids, emulsifiers, permeability modifiers and antifoaming agents for processing liquids, etc.
No. 32, No. 1,221,980, U.S. Patent No. λ99
Specifications of Patent No. 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., especially 0.5 to 2
Examples include silica gel having a particle size of 0 pm, and polymethyl methacrylate polymer having a particle size of 0.5 to 20 μm.

The silver halide photographic material containing a tetrazolium compound in the silver halide emulsion layer and/or other hydrophilic colloid layer of the present invention may be developed in the presence of a compound represented by the following general formula [■]. is preferred.

General formula (m) L9 [In the formula, s R1 is a nido group at the 5- or 6-position, R2
represents a hydrogen atom or a C1 to C5 lower furkyl group. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion. ] Specific examples of the compound represented by the general formula (m) include 5-nitroindazole and 6-nitroindazole, but the present invention is not limited thereto in any way.

The compound represented by the general formula [■] 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 the general formula [■] is the developer 11! Hit,
Concentrations range from about 11 g to 1.000 g, preferably from about 50'q to 300119 g.

Examples of the developing agent for the black-and-white silver-genide photographic light-sensitive material of the present invention include the following. This developing agent can be used together with the compound represented by the above-mentioned general formula [m].

HO+CH=CH-+nOHnOH Main developing agents include hydroquinone, and in addition, catechol, birogal and its derivatives, ascorbic acid, RP hydroquinone, pmo/-hydroquinone, isopropylhydroquinone, and toluhydroquinone. , methylhydroquinone, 2゜3-dichlorohydroquinone, 2.5-diethylhydroquinone, 2,3-dibromo/1ido-quinone, 2.5-dihydroxy7cetophenone, 2゜5-diethylhydroquinone, 2,5 −
Di-p-phenethylhydroquinone, 2,5-dibenzoylamide/hydro-? /n, catechol, 4-kuji-
Catechol, 3-phenylcatechol, 4-phenyl-
Examples include catechol, 3-methoxycatechol, 4-7 cetylpyrogallol, 4-(2-human p-xybesozoyl)pyrogallol, and sodium 7scorbate.

In addition, HO+ CH= CI +rlNH2fJi expression agents include ortho and rose 7-minophenol or 7-minovirazopone, and 4-7ξnophenol, 2-amino-6-phenylphenol, 2-amino- 4-riρ-6-phenylphenol, 4-74
No 2-Phenylphen/-le, 3゜4-Sif! Nophenol, 3-methyl-4,6-diamitphenol, 2.
4-Sifumylsorcinol, 2,4.6-Drifuminophenol, N-7,2°-2-7K/7x,/
-/k, N-/-b F' p-ruxyethyl-rouminophenol p-hydroxyphenyl 7
i-inoacetic acid, 2-7minona7tol, etc.

Furthermore, as the H2N + C= C+rINH2ffi developer, for example, 4-7 minnow 2-methyl-N, N-
Diethyl 7-niline, 2,4-diamino-N, N-diethylaniline, N-(4-7mi/-3-methylphenyl)
-morpholine, p-phenylenediamine, 4-amino-
N,N-dimethyl-3-human-xy7niline, N,N,
N,N-tetramethylpara-7enylenediamine, 4-amino-N-ethyl-N-(β-hydroxyethyl)-7
Nilin, 4-amino-3-methyl-N-ethyl-N-(
β-hydroxyethyl)-7niline, 4-7 minnow N-
Ethyl-(β-methoxyethyl)-3-methyl-7 diphosphorus, 4-7mi/-3-methyl-N-ethyl-N-(β-
Methylsulfone (7midoethyl)-aniline), 4-7minor N-dimethyl-N-r-sulfobutylaniline, 1-
(4-7minophenyl)-pyrulysine, 6-7ζ No 1
-ethyl, 1,2゜3.4-tetrahydroquinone, 9
-7 Minoiulolidine, etc.

Examples of the developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-human-oxymethyl-3-pyrazoliton, l-7enyl-3 such as 4-methyl-4-hydroxymethyl-3-pyrazolidone
-Pyrazolidones, 1-7enyl-4-amino-5-pyrazolone, 1-(p-7minophenyl)-3-7minor-2-pyrazoline, 1-phenyl-3-methyl-4-7minor-5-pyrazolone, 5 -7 minouracil, 5-ami/
-2,4,6-)rihydroxyphyrimidene and the like.

Others: The Theory Op. by T. H. James
The Photographic Booths 4th Edition
ory of the Photographic P
rocess, Fourth Edition) 2nd
pp. 91-334 and Journal of the American Gemical Society.
he American Chemical 8ocl
Ety) Vol. 73, p. 3, 100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of 2 m or more, but it is preferable to use them in combination of 2 m or more. Furthermore, even if a sulfite salt such as potassium sulfite or sulfite is used as a preservative in the developer used in the present invention, the effects of the present invention will not be impaired. In addition, hydroxylamine or hydrazide compounds may be used as preservatives.In addition, caustic alkali, carbonate alkali, or amine used in general black and white developers may be used to adjust the pH and provide a buffer function. , and inorganic development inhibitors such as bromkali and organic development inhibitors such as penztriazole,
Metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzylfurfur, and polyalkylene oxide, surfactants such as sodium furkylarylsulfonate, natural saponins, sugars, or furkyl esters of the above compounds. It is optional to add hardening agents such as glutaraldehyde, formalin and glyoxal, and ionic strength adjusting agents such as sodium sulfate.

The developer used in the present invention may contain flukanolamines or glyfurs as organic solvents. As the above-mentioned flukanolamine, for example, monoethanolamine, jetanolamine, triethanolamine, and triethanolamine are preferably used. The usage amount of these flukanolamines is currently **I
I! Hit 5-? 500 #, preferably 20-20
It is 0g.

In addition, the above-mentioned glyfurs include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, l,4-butanediol, l,5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is 5 to 500.9 parts per developer, preferably 20 to 200.9 parts per developer. These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention has the above-mentioned y!
By developing with a developer containing AgI and an inhibitor, it is possible to obtain photosensitivity properties that are much more stable than those of K.

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
0°C or less is preferable, II K is preferably around 30°C,
Further, the development time is generally completed within 3 minutes, but particularly preferably within 40 seconds, which often brings about good results. Processing steps other than development, such as washing, stopping,
Stable, established, and more essential! It is optional to adopt steps such as preduralization and neutralization depending on the situation, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

Examples> A silver chlorobromide emulsion was cracked using the following solutions A, B, and C.

[Solution person]

Ossein gelatin 17.9 Polyisopropylene-polyethylene oxydisuccinate sodium salt 51I7 10% ethanol solution Distilled water 1280 cc [Solution B] Silver nitrate 170.9 Distilled water 410 yLl
[Solution C] Sodium chloride 40.9!
i Potassium bromide 35.7
g polyisoprho pyreneoxydisuccinic acid ester sodium salt 10% ethanol solution 3M ossein gelatin 11.9 Distilled water
407d solution person 40″O
After keeping warm, sodium chloride was added so that the EAg value was 160 mv.

Next, using the mixing agitator described in JP-A-57-92523 and JP-A-57-92524, the solution B was prepared by a double jet method.
and solution C were added.

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 BAg constant.

The BAg value was 3i1/5 minutes after the start of addition from 160 mv.
l! The EAg value was 120 using an aqueous solution of IJ chloride.
mvlC was varied and maintained at this value thereafter until completion of mixing.

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

Table 1: For the measurement of BAg values, a metal silver electrode and a double-junction saturated Ag/AgC1! A comparison electrode was used (the structure of the electrode was a double junction electrode disclosed in JP-A-57-197534).

Further, a variable flow rate G-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 adjusted to 3. OK, keep it constant 3
% 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.
An aqueous solution of ossein gelatin 6001j (containing 31 ossein gelatin) was added and dispersed by stirring at 55° C. for 30 minutes, and then 750 cc Kll was prepared.

Next, this emulsion was subjected to total sulfur sensitization, and 6-methyl-4-human-oxy-1,3°3a,7-chitrazaindene was added as a stabilizer. The emulsion was divided and as shown in Table 2, the compounds of the general formula [E] according to the present invention or the sensitizing dyes (CI) -ia3~(k) shown below for comparison were added.
3 x 10-'mol 1 mol Ag was added to each emulsion for color sensitization, and a tetrazolium compound [Ir]-2 was added to each emulsion.
700 my/Ag 1 mol was added, sodium n-dodecylbenzenesulfonate sooig 9/Ag 1 mol, styrene-maleic acid copolymer 211/Ag 1 mol were processed, and polyethylene tere-7-thalerate fluoride was processed.
Upper KAg 3.51,'t La+ 711011 /
m” K.At that time, the amount of gelatin was 1.0
1i/m” as a vehicle.
A hardening film protective layer containing 30119/ml of sodium (3-inpentyl)succinate 2-sulfonate and 25 tonnage/rrl of formalin as a hardening agent was coated in multiple layers.

Table 2 Comparative sensitizing dye CH2C02H Co["I:l -(41H CI:l -(gl CI)-(hl 2H6 Meng(I) -(i) CI) -1) (I) -Tkl Obtained Three pieces of each sample were taken, and one piece was exposed to tungsten light using a photosensitive needle and an optical wedge. The shaded areas were exposed to xenon light using a 150L (150L).The remaining piece was not exposed and was subjected to the following treatment.

The above 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 40/cm.

[Development processing conditions]

(Process) (Temperature) (Time) Development 28℃ 30 seconds Fixing 28℃ 20 seconds Washing with water 20℃ 20 seconds Drying 40℃ 20 seconds [Developer composition] (Composition person) (composition) When using a developer, add the above composition to 500 wJ of pure water.

It was used by dissolving it in the composition and finishing it to 1/2.

For developed samples subjected to wedge exposure, draw a photographic characteristic curve and calculate the sensitivity at optical density 25 as sample/I.
Relative values are calculated based on 61, and gamma is an optical density of 1.0.
The 10 value of the straight line part from to 25 is shown.

For those whose nets were photographed using a printing plate-making camera using xenon light, the quality of the formed nets (dot quality) was evaluated.

The dot quality is determined by visually judging the state of the fringe (blur) that occurs around the halftone dot when the area of the halftone dot and the area of the clear part are equal to 1 or 50%. The evaluation was based on the display.

That is, "5" is excellent and 61" is extremely bad. If the 50% dot quality is less than 13", it 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'' indicating no color and 1'' indicating a strong orange residual color. Ta. For general plate making, residual color below 3" is at a level that is considered a major drawback.

As shown in Table 3, only the samples color-sensitized with the sensitizing dye of the general formula CI) according to the present invention had high relative sensitivity, extremely high contrast, and no residual color. It can be seen that the number of samples is small.

<Example 2> A sample was prepared in exactly the same manner as in Example 1.

However, the sensitizing dyes (I)-4 and (Ill-24) are shown in Table 4.
Additions were made in the amounts shown. Examples of tetrazolium salts include those of the general formula []] according to the invention K, or contrast compounds ((U)a-e) having a substituent with a positive Hammett's σ value or having no substituent at all. was added at a concentration of 700 f/1 mole of Ag as shown in Table 4. After sample preparation Example 1
Three samples were prepared in the same manner as above, and the wedge-exposed shading indicates exposed and residual color samples.

Table 4 Hjt″” y “j ′A* ' * * '” '
E'A9'''+,ru.
/-m-, there is a margin゛.

/-knot σ of the substituent of the above comparison compound, the value is CF3
: 0.54, NO3: 0.7g, 00 parts 3: 0
．． It is 50.

As shown in Table 5, the samples of the present invention (/1623 to 33) have low capri, high contrast, and excellent performance with little residual color.

〔Effect of the invention〕

As is clear from the above examples, the general formula [”I
] Unlike sensitizing dyes with similar structures, the compound represented by the formula [''U] forms a specifically high-contrast image when used in combination with the compound represented by the general formula [''U], and is free from dye staining. As a result, images with extremely high contrast can be obtained even with short processing using a developer with high sulfite ion concentration and good stability, and silver halide photographic sensitizers with extremely little dye staining after processing. It became possible to manufacture the material.

Applicant Roku Konishi Photo Industry Co., Ltd. Proceedings Amendment 1/Case 0 Display /θ-//2 Fq 1985 1985 Silver Halide Photographic Materials 3, Person making the amendment Relationship to the case Patent Applicant Address 26-2 Nishi-Shinjuku IT, Shinjuku-ku, Tokyo 191 Sakura-cho, Hino-shi, Tokyo Konishiroku Photo Industry Co., Ltd. (Telephone 0425-83-15)
21) - Patent Department 4, date of amendment order 5, "Detailed Description of the Invention" column 6 of the specification to be amended, content of the amendment 1) Structure of compound example (1]-11 in the lower part of page 19 of the specification Correct the expression as follows:

2) "F spreading agent" on page 57, line 10 of the same was corrected to "spreading agent," 3) No. 61 of the same
Correct the structural formula in (1)-h in the middle of the page as follows.

4) Page 63, line 19 Correct "2g" to "5g".

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 milk 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, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, or a substituent -(CH_
2) represents −_nA. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or a lower alkoxy group, and n represents an integer value of 1 to 4. R^3 and R^4 may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a chlorine atom or a carboxy group. ] General Formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. , and X^■ represents an anion. However, R^5,
R^6 and R^7 are never hydrogen atoms at the same time. ]